Azo compounds and methods for producing same



United States Patent 3,139,421 AZO COMPOUNDS AND METHODS FOR PRODUCING SAME Edward F. Elslager, Donald F. Worth, David B. Capps,

and Leslie M. Werbel, all of Ann Arbor, Mich., assignors to Parke, Davis & Company, Detroit, Mich., a corporation of Michigan No Drawing. Filed Mar. 14, 1960, Ser. No. 14,523 6 Claims. (Cl. 260-154) This invention relates to a novel class of azo compounds and salts thereof and to methods for obtaining same. More particularly, it relates to novel 4-(dialkylaminoalkylamino)-l-naphthylazo heterocyclic compounds and non-toxic acid-addition salts thereof which possess anti-parasitic activity.

The novel 4 (dialkylaminoalkylamino)-1-naphthylazo heterocyclic compounds with which the present invention is concerned have in their free base form the formula N=NHET where Y represents a radical of the formula R1 AN or a radical of the formula -(c1rm-(JH A represents an alkylene radical containing between 2 and 8 carbon atoms inclusive, or an alkylene radical containing more than 2 and less than 7 carbon atoms in which one of the methylene groups not attached to the nitrogen atoms is replaced by O-, S, -=CHOH, =COH- (lower alkyl), =N(lower alkyl) or =CH(diloweralkylaminoalkyl); R represents hydrogen, a lower alkyl radical, a halogen atom, or a lower alkoxy radical, said R group can be attached to the 5th, 6th, or 7th positions of the naphthylene nucleus; R and R each represents an alkyl radical, a cycloalkyl radical, a hydroxyalkyl radical, or an alkoxyalkyl, said radicals containing fewer than 7 carbon atoms, the allyl or methallyl radicals, or a lower dialkylaminoalkyl radical containing 3 to 7 carbon atoms inclusive, or in combination with -N represent a heterocyclic radical having fewer than 10 carbon atoms such as e.g. a pyrrolidyl, piperidinyl, hexamethyleneiminyl, morpholinyl, piperazinyl, homopiperazinyl or decahydroquinolyl radical, said heterocyclic radical optionally bearing lower alkyl, lower hydroxyalkyl, lower alkoxyalkyl, hydroxy, lower alkoxy, amino, or lower dialkylaminoalkyl substituents; f represents an integer from 0 to 3 inclusive, g and h represent integers such that g+h=3 or 4; R represents a lower alkyl, lower hydroxyalkyl, lower alkoxyalkyl, or a lower dialkylaminoalkyl radical; and HET represents a heterocyclic radical of fewer than carbon atoms, a carbon atom of which is bound to the azo nitrogen atom, said heterocyclic radical may carry one or more substituents such as keto, hydroxy, lower alkyl, lower hydroxyalkyl, lower aminoalkyl, halo, phenoxy, acyl, sulfo, carboxy, thio, sulfonamido, sulfonyl, imino, phenyl, lower alkoxy, nitro, or amino radicals. Examples of suitable heterocyclic radicals are the furyl, thienyl, pyrryl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isooxazolyl, hexamethyleneiminyl, oxa- 3,139,421 Patented June 30, 1964 zinyl, thiazinyl, triazolyl, oxadiazolyl, thiadiazolyl, dioxanyl, oxathiolyl, oxadiazolyl, dithiinyl, oxathiinyl, pyranyl, thiapyranyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, or the tetrazolyl radicals, their N-oxides and benzo-, and naphtho-condensed ring systems.

In accordance with the invention, the novel 4-(dialky1- aminoalkylamino)-1-naphthylazo heterocyclic compounds of the above formula and their acid-addition salts can be produced in a number of ways.

For example, the products of the invention can be prepared by coupling an a-naphthylamine havingin free base form the formula with a diazonium compound of the formula [NEN-HET]+AC.

In the above formula Acrepresents the anion of an acid or the OH- ion and R, Y, and HET have the same meaning as given above. Preferably, the reaction is conducted under acidic or neutral conditions (pH7), although if desired, basic conditions can be employed. In carrying out this condensation it is generally satisfactory to employ substantially equivalent quantities of the reactants in the presence of a suitable solvent. Suitable solvents for the reaction are aqueous mixtures of water-miscible aliphatic alcohols, such as methanol, ethanol and propanol; tetrahydrofuran, N,N-dimethylacetamide, N,N-dimethylformamide, simple organic acids such as formic acid, acetic acid, propionic acid and the like; or the acid furnishing the anion represented by Ac-. Where it is desired to carry out the reaction at a controlled pH, a suitable buffer system may be employed. In general, the time and temperature of the reaction are not critical; however, heating is to be avoided, and a temperature less than 15 C. is preferred.

The diazonium compounds of the above formula can be conveniently prepared in situ, by the reaction of an amine of the formula NH -HET with an alkali nitrite such as e.g. sodium nitrite in an acid medium (pH 7) or by other methods known to organic chemists, and added to the coupling reaction mixture containing the desired a-naphthylamine of Formula I.

The a-naphthylamines of the Formula I employed as starting materials in this reaction can be prepared in various ways.

For example, they can be prepared by aminoalkylation of an a-naphthylamine of the formula or an alkali metal salt thereof with an aminoalkylating agent of the formula R1 XA-N/ or of the formula Z- (C H2) -0 H N-R;

3 wherein X represents a halogen atom or the CH CH- H (or lower alkyl) II (or lower alkyl) H-C-B-N and an a-naphthylamine of the formula in a solvent medium. Suitable solvents for the reaction are benzene, toluene and the like. The reaction is favored by an acid catalyst such as e.g. p-toluene sulfonic acid, and by temperatures in excess of 50 C. and is preferably carried out between 50 and 150 C. The Schilf bases so formed can be reduced catalytically without isolation or purification from the reaction mixture. In the above formulas R, R and R have the aforementioned significance and B represents an alkylene radical containing between 2 and 7 carbon atoms inclusive, or an alkylene radical containing more than 2 and less than 6 carbon atoms in which one of the methylene groups not attached to the nitrogen atoms is replaced by --O, S, =CHOH, =CH(dialkylaminoalkyl) or =N(lower alkyl).

Additionally, the a-naphthylamines of Formula I can be prepared by a replacement reaction between a compound of the formula or of the formula 2N( 2)1- I N- a and the hydroxyl group on an a-naphthol of the formula BIL) .4 The reaction is favored by temperatures of -175" C. and is preferably carried out in a sealed container in an aqueous medium and in the presence of an agent such as sulfur dioxide, sodium bisulfite or sodium hydrosulfite. In the above formulas A, R, R R R f, g, and it have the aforementioned significance.

Another process for the preparation of the compounds of the invention comprises reacting an azo compound of the formula IfH-A-Hal =N-HET with an amine of the formula wherein Hal represents a hologen atom and A, R, R R and HET are defined as hereinbefore. The reaction is preferably carried out in a solvent medium. Some suitable solvents for this purpose are aliphatic alcohols such as ethanol, isopropanol, pentanol, glycols or the amine employed in the reaction. The relative proportions of the reactants is not critical; however, best results are obtained when an excess of the amine is employed. The reaction is favored by temperatures in excess of 50 C. and preferably carried out between 50 and C.

The azo compounds of the above formula employed as starting materials in this reaction are conveniently prepared by the coupling of a compound of the formula NH-A-Hal with a diazonium compound of the formula [NEN-HET] +Acwherein Hal, A, R, and HET have the aforementioned significance and Acrepresents the OH ion or the anion of a hydrohalic acid. Preferably, the reaction is conducted under acidic or neutral conditions (pH g7), although if desired, basic conditions can be employed. In carrying out this condensation it is satisfactory to employ substantially equivalent quantities of the reactants in the presence of a suitable solvent. Suitable solvents for the reaction are aqueous mixtures of water-miscible aliphatic alcohols, such as methanol, ethanol and propanol; tetrahydrofuran, N,N-dimethylaeetamide; simple organic acids such as formic acid, acetic acid, propionic acid and the like; or an excess of the acid furnishing the anion represented by Ac. Where it is desired to carry out the reaction at a controlled pH, a suitable buffer system may be employed. In general, the time and temperature of the reaction are not critical; however, heating is to be avoided, and a temperature less than 15 C. is preferred.

The diazonium compounds of the above formula can be conveniently prepared in situ, by the reaction of an amine of the formula organic chemists, and added to the coupling reaction mixture containing the desired compound of Formula It.

The compounds of the invention can also be produced by hydrolysis of a compound of the formula N=N-HE T wherein the group is particularly susceptible to hydrolytic cleavage by acidic or basic hydrolytic agents under mild conditions. In the above formulas R represents the hydrogen atom or a perhaloalkyl radical such as e.g. ---CF;,, and R, Y, and HET have the aforementioned significance. Where R represents a perhaloalkyl radical, the hydrolysis is preferably effected by dissolving the starting material in a watermiscible inert organic solvent such as methanol, adding an aqueous solution of an alkali metal hydroxide, conveniently and aqueous solution of sodium or potassium hydroxide having a normality of about 1 to 3, and allowing the reaction mixture to stand (with or without stirring) at about room temperature until the reaction is completed. Where R represents the hydrogen atom, hydrolysis is preferably conducted in the presence of a mineral acid such as e.g. hydrochloric acid under similar reaction conditions.

The amides employed as starting materials in this process are novel per se and can be prepared by a process which comprises acylation of a nitro compound having the formula IfH-Y with an acid of the formula i HO-iI-Ri or a functional derivative thereof to yield an amide of the formula subjecting said amide to hydrogenation in the presence of a catalyst such as e.g. Raney nickel to yield an amino compound of the formula 6 converting the said amino compound to a diazonium compound, and coupling the said diazonium compound with a suitable hetcrocyclic compound. In the above formulas Y, R and K, have the aforementioned signific'ance. Where R represents the perhaloalkyl group such as e.g. trifluoromethyl, the acylation reaction is conveniently effected by employing the acid anhydride in a solvent medium such as e.g. N,N-dimethylformamide. Where R represents a hydrogen atom, acylation is preferably effected using a formic acid-acetic-anhydride mixture. Acylation with the latter agent is favored by increased temperatures, preferably between 50-125 (1., whereas the acylation using the perhaloalkanoic acid anhydride proceeds readily at about 2550 C.

The conversion of the free -NH group to the diazonium salt proceeds readily under mild acidic conditions in the presence of an alkali nitrite such as e.g. sodium nitrite, preferably at a temperature under 15 C. The coupling of the diazonium salt and the heterocyclic component can be elfected under basic or acidic conditions. In general, where the heterocyclic component is acidsensitive, the formamide derivative is employed and the coupling conducted under neutral or basic conditions (pH 57 Where the hetcrocyclic component is alkalisensitive, the coupling reaction is preferably conducted under acidic conditions (pH g7) and a perhaloalkanoylamide derivative, preferably the trifiuroacetamide derivaltive, is employed. The time and temperature of the coupling reaction are not critical, however, best results are obtained when the reaction is allowed to proceed at a temperature less than 15 C. Preferred solvent for the reaction is water or aqueous mixtures of water-miscible alcohols such as methanol, ethanol, propanol and the like. If desired, after the coupling reaction has proceeded to completion, the azo-amide compounds can be hydrolzyed to the azo products of the invention without isolation or purification by adjusting the pH and temperature of the mixture to the preferred range.

As mentioned above, the compoundsof the invention possess valuable anti-parasitic properties. More particularly, the compounds are active against Schistosoma mansom, a causative agent of schistosomiasis. They are active when administered orally. In addition, the compounds of the invention are valuable intermediates in the preparation of other valuable chemical compounds possessing anti-parasitic activity.

The free bases encompassed herein can also be employed in the form of their addition salts with pharmaceutically acceptable acids, the term pharmaceutically acceptable acids designating acids capable of being employed in the production of salts suitable for pharmaceutical use even though, like irritant and corrosive acids, they are not acceptable for pharmaceutical use in and of themselves. The expression salts with pharmaceutically acceptable acids refers to chemical structure rather than to method of formation, and includes such salts whether formed by neutralization or other salt forming means. Some examples of the many organic and inorganic acids which can be used to produce the corresponding acid-addition salts are hydrochloric, hydrobromic, hydroiodic, sulfuric, phosphoric, oxalic, cholic, sulfamic, naphthalene-1,5-disulfonic, phenoxyacetic, lactic, tartaric, gluconic, alginic, citric, succinic, maleic, malonic, adipic, mandelic, oleic, tannic, ethylsulfuric, penicillinic, benzoic, 5,5-naphthalenedisalicylic, 3- and 5- phenylsalicylic, 3-hydroxy-2-naphthoxy, 4,4'-methylenebis (3 hydroxy 2 naphthoxy), 1,4,5,8 naphthalenetetracarboxylic, 4-biphenylcarboxylic, terephthalic, pyromellitic, 8-hydroxy-7-iodo-5-quinolinesulfonic, cyclopentylpropionie, cyclohexanecarboxylic, arsanilic, arsonic acid and the like. Salts of the free bases of the invention with inorganic antimony derivatives such as e.g. antimony trichloride, and with compounds known to possess activity against schistosomiasis such as phthalic acid, mono-4-(3'- chloro-4'-methylphenyl)-piperazide, maleic acid mono-4 (3' chloro 4' methylphenyl) piperazide, pyridine-2,3- dicarboxylic acid mono-4-(3'-chloro-4-methylphenyl)- piperazide, succinic acid mono-4-(3-chloro-4-methylphenyl)-piperazide, oxalic acid mono-4-(3'-chloro-4- methylphenyl) piperazide, maleic acid mono-4-(3'- bromo-4-methylphenyl)-piperazide, adipic acid mno-4 (3' chloro 4' methylphenyl)-piperazide, glutaric acid rnono 4 (3' chloro 4 methylphenyl) piperazide, terephthalic acid mono-4- 3 '-chloro-4'-methylphenyl piperazide, diglycollic acid mono-4-(3-chloro-4'-methylphenyl)-piperazide, N,N'-[heptamethylenebis (oxy-pphenylene)]-diglycine, N,N'-[heptamethylenebis (oxy-pphenylene)] di-b-alanine, [heptamethylenebis-(oxy-pphenylene nitrilo) ]-tetraacetic acid, and organic antimony derivatives such as 2-hydroxy-5-oxo-l,3,2-dioxastibiolane- 4-glycolic acid, 2-(4,6-disulfo-l,3,2-benzodioxastibiol-2- yloxy)-1-phenyl-3,5-disulfonic acid, and antimony-2,3-dimercaptosuccinate are of particular interest.

The invention is illustrated, but not limited, by the following examples:

Example 1 A solution of 41.2 g. (0.325 mole) of S-arninouracil in 11. of 50% ethanol and 85 ml. (1 mole) of concentrated hydrochloric acid is cooled to 0 C. The amine is diazotized by the slow, portion-Wise addition of a solution of 22.4 g. (0.325 mole) of sodium nitrite in 200 ml. of water. The mixture is stirred 15 minutes at 0 C., then added slowly at 0 to 5 C. to a solution of 78.7 g. (0.325 mole) of 1-(2-diethylaminoethylamino)-naphthalene in 11. of 95% ethanol and sufiicient concentrated hydrochloric acid to make the solution acidic to Congo red. The deep purple solution which forms immediately changes slowly to a green suspension as the hydrochloride salt begins to precipitate. The suspension is stirred about 1 hour at 0 C. The pH is adjusted to approximately 8 by the addition of sodium hydroxide solution and the red product is collected by filtration. This is the desired 5 [4 (2 diethylaminoethylamino) 1 naphthylazo1- uracil. of formula Crystallization from ethanol gives shiny red crystals, M.P. 2l0-211 C. (dec.).

The hydrochloride salt is prepared as follows: 3.3 g. of the base is dissolved in boiling ethanol and the solution is filtered into 200 ml. of ethanolic hydrogen chloride. The resulting deep purple suspension is heated to boiling and allowed to cool overnight. The dihydrochloride salt which precipitates is collected by filtration and dried in vacuo at 65 C.; M.P. 200-203" C.

The acid addition salt with 4,4'-methylenebis(3-hydroxy-2-naphthoic acid) can be prepared according to the following procedure: 200 g. (0.5 mole) of 5-[4-(2-diethylaminoethylamino)-1-naphthylazo]-uracil and 97 g. (0.25 mole) of 4,4-methylenebis(3-hydroxy-2naphthoic acid) are dissolved in 2.5 l. of dimethylformamide. The solution is cooled to approximately 10 C. and poured slowly with vigorous stirring into 7.5 l. of cold water. The precipitate is collected by filtration, washed thoroughly with water and methanol, and dried in vacuo. The red salt thus obtained, M.P. 210-215 C., is the desired 5 [4 (2 diethylaminoethylamino) 1 naphthylazo]- uracil, salt with one-half formula weight 4,4'-methylenebis(3-hydroxy-2-naphthoic acid), of formula,

In like manner, the following related compounds can be prepared, starting from S-arninouracil and an equivalent quantity of the appropriate l-(dialkylaminoalkylamino)-naphthalene:

5- [4- 2-dimethylaminoethylamino) 1 -naphthylazol] uracil 5- [4- (2-diisopropylaminoethylamino)-1-naphthylazo] -uracil 5- [4-( Z-dibutylarninoethylamino) -1-naphthylazo] uracil 5- [4- (2-diisobutylaminoethylamino) -1-naphthaylazo] uracil 5- [4-( 3-dimethylaminopropylamino) -1-naphthylazo] uracil 5- [4- 3 -diethylaminopropylamino)-1-naphthylazo] uracil 5- [4-(2-dimethylamino-l-methylethylamino) -1- naphthylazo] -2,4-pyrimidinediol The starting material, 1-(Z-diethylaminoethylamino)- naphthalene, can be prepared as follows: a mixture of 572 g. (4 moles) of l-naphthylarnine, 690 g. (4 moles) of 2-diethylaminoethylchloride hydrochloride, 1250 g. (9 moles) of anhydrous potassium carbonate, 3 l. of benzene and 20 g. of copper-bronze powder is stirred and boiled under reflux for 18 hours. The mixture is cooled and 5 l. of 5% sodium hydroxide and 1 l. of ether are added. The mixture is stirred vigorously for one-half hour, the layers are allowed to separate and the aqueous layer is siphoned off. The alkaline solution is extracted with several portions of ether, benzene or chloroform, and the combined organic extracts are added to the benzene-ether layer. The combined solvent mixture is washed twice with water, once with saturated sodium chloride solution and dried over anhydrous magnesium sulfate. The drying agent is collected by filtration and the filtrate concentrated in vacuo on the steam bath. Vacuum distillation of the residue through a 10-inch Vigreux column gives the desired 1-(Z-diethylaminoethylamino)-naphthal ene as a pale yellow oil, B.P. -172 C./ 1.5 mm., n 1.5903.

The other intermediate 1-(dialkylaminoalkylamino)- naphthalenes can be prepared by the procedures described under Examples 1 through 15 herein.

Example 2 A solution of 12.0 g. (0.025 mole) of N-[4-(2,6-diamino 3 pyridylazo) l naphthyl] N (2 diethylaminoethyl)-a,a,a-trifiuoroacetamide is dissolved in 250 ml. of Z-propanol, filtered, and treated with 25 ml. (0.050 mole) of 2 N sodium hydroxide solution in methanol and 5 ml. of water. Stirring is continued for 25 hours, after which time excess Dry Ice is added and the mixture is diluted with an ice and water mixture to a volume of 1 l. The precipitate is collected, by filtration and the filtrate is concentrated to a volume of approximately 400 ml., during which process a precipitate appears. This is collected by filtration and combined with the previous solid. This product is dissolved in 300 ml. of 2-propanol, filtered, and the filtrate is concentrated to 250 ml. and treated with 12 ml. of a 2 N 2-propanolhydrogen chloride mixture. The precipitate is collected by filtration and crystallized from a dimethylformamide-2-propanol mixture. The black crystals thus obtained, M.P. 234 C. (dec.), are the desired 2,6-diamino-3-[4-(2-dimethylaminoethylamino)-l-naphthylazo]pyridine, monohydrochloride, of formula,

By a similar procedure, the following related compounds can be prepared, starting from the appropriate l-(alkylaminoalkylamino)-naphthalene via the N-[4-(heterocyclicazo)-l-naphthyl]-N-(alkylaminoalkylamino) a,ot,ottrifluoroacetamides:

1-{3-[4(2,6-diamino-3-pyridylazo)-1-naphthylamino] propyl}-piperidine, hydrochloride.

2,6-diamino-3- [4-( 3-diethylaminopropylamino) -1- naphthylazo]-pyridine, hydrochloride.

2,6-diamino-3- [4- 2-diethylaminoethylamino -7-nitrol-naphthylazoJ-pyridine, hydrochloride.

2,6-diamino-3-{4-{ 3- [bis- (Z-methoxyethyl-amino] -2,2- dimethylpropylamino}- l-naphthylazo}-pyridine, hydrochloride.

4-amino-3- 4-( 3-diethylaminopropylamino -1-naphthylazol]-2,6-pyridinediol, hydrochloride.

2,4,6-triamino-3- [4- (Z-diethylaminoethylamino) -1- nnphthylazol-pyridine, hydrochloride.

2-amino-6- 2-diethylaminoethoxy) -3- [4- 2-diethylaminoethylarnino) -1-naphthylazo] -pyridine, dihydrochloride.

4-{2-{ l -{2- [4- (2,6-diamino-3-pyridylazo) -1-naphthylamino] -ethyl}-4-piperidyl}-ethyl}-morpholine, dihydrochloride.

N [4 (2,6 diamino 3 pyridylazo) 1 naphthyl]- N (2 diethylaminoethyl) t,0t,0t trifiuoroacetamide, employed as a starting material in the above procedure, is prepared as follows: a mixture of 46 g. (0.22 mole) of 1- chloro-4-nitronaphthalene and 77 g. (0.66 mole) of N,N- diethylethylenediamine is heated on the steam bath until an exothermic reaction occurs. The temperature reaches 140 C., then drops slowly to 110 C., whereupon heating is resumed for 2 hours. The hot melt is poured with stirring into 750 ml. of water containing 35 ml. of concentrated ammonium hydroxide and ice. The aqueous phase is separated, the residue triturated with warm water, and the residue crystallized from 2-propanol. This is the desired intermediate, N,Ndiethyl-N-(4-nitro-1-naphthyl)- ethylenediamine, yellow platlets, M.P. 80-81 C.

Subsequently, a solution of 13.5 g. of trifluoroacetic anhydride in 40 ml. of dimethylformamide is added to a stirred solution of 14.4 g. of N,N-diethyl-N'-(4-nitro-1- naphthyl)-ethylenediamine in 90 ml. of dimethylformamide over a period of 30 minutes. Stirring is continued for 1 hour and the reaction mixture is poured into 1 l. of ice and water containing 150 ml. of 1 M sodium bicarbonate solution. The mixture is extracted with three 2 1. portions of ether and the combined ether extracts are washed with water and dried over anhydrous magnesium sulfate. The desiccant is collected by filtration and the ether is removed in vacuo to give the desired intermediate N (4 nitro-1-naphthy1)-N-(2-diethylaminoethyl)-a,u,atrifluoroacetamide as a viscous oil, which is used directly in the subsequent reaction without further purification.

The N (2-diethylarninoethyl)-N-(4-nitro-1-naphthy1)- a,a,ot-trifiuoroacetamide (16 g.), is dissolved in 250 ml. of

methanol and 40 ml. of 1 N methanolic hydrogen chloride and hydrogenated in the presence of 1 g. of Raney nickel catalyst at 25-35 C. under 25-55 p.s.i.g. of hydrogen. The catalyst is collected by filtration and the filtrate evaporated under reduced pressure to give a mushy crystalline residue which is diluted with ether, filtered, and the precipitate washed thoroughly with ether. Crystallization from ethanol gives the desired N-(2-diethylaminoethyl)- N (4 amino 1 naphthyD-trifiuoroacetamide, monohydrochloride as fine white needles, M.P. 216218 C.

To a stirred solution of 9.75 g. (0.025 mole) of N-(2- diethylaminoethyl) N (4-amino-1-naphthyl)-trifluoroacetamide, monohydrochloride, in g. of water and ice containing 4.5 m1. of concentrated hydrochloric acid is added 25 n11. of 1 M sodium nitrite over a period of 5 minutes. The mixture is stirred at 0 C. for 5 minutes and added immediately to a solution of 2.8 g. (0.025 mole) of 2,6-diaminopyridine in 5.5 ml. of concentrated hydrochloric acid and 275 g. of ice and water. After stirring for one hour at 1-12 C. and one hour at 12-18 C., a solution of 8 ml. of concentrated ammonium hydroxide diluted to ml. with water is added and the orange solid which separates is collected by filtration, Washed with 200 ml. of water containing a few drops of concentrated ammonium hydroxide, and dried in vacuo. This is the desired intermediate, N-[4-(2,6-diamino-3- pyridylazo)-l-naphthyl]-N-(2-diethylaminoethyl) u,a,oztrifiuoroacetamide.

The other N (4 pyridylazo-l-naphthyl)-N-(dialkylaminoalkyl)-a, x,a-trifluoroacetamides are prepared in a similar manner from the appropriate aminopyridine and N dialkylaminoalkyl-N-(4 amino-l-naphthyl)-a,a,a-trifluoroacetamide compounds.

Alternatively, 2,6 diamino-3 [4-(2-diethylaminoethylamino)-1-naphthy1azo]-pyridine, monohydrochloride and related compounds can be prepared from N-(Z-diethylaminoethyl) -N-(4-amino-1-naphthyl) -formamide according to the following procedure: A mixture of 3.5 ml. of formic acid, 8.4 ml. of acetic anhydride, and 50 ml. of tetrahydrofuran is heated on the steam bath for two hours. Upon cooling 5.74 g. (0.02 mole) of N,N-diethyl-N' (4-nitro-1-naphthyl)-ethylenediamine is added, and the resulting solution is stirred and heated under reflux for 24 hours. The solvent is removed in vacuo and the residue suspended in excess aqueous sodium hydroxide solution and extracted with ether. The ether extracts are dried over anhydrous sodium sulfate, the drying agent is collected by filtration, and the solvent removed in vacuo. The residual yellow oil is the desired intermediate, N-(2- diethylaminoethyl) N (4-nitro-1-naphthyl)-formamide, which is used directly in the next step without further purification.

The above formyl derivative is subsequently dissolved in 3 00 ml. of methanol and hydrogenated at an initial hydrogen pressure of 44 p.s.i.g. in the presence of 1 g. of Raney nickel catalyst. The catalyst is collected by filtration and the solvent removed in vacuo. The residual oil is cooled to room temperature, dissolved in 2-propanol, and treated with a 2-propanol-hydrogen chloride mixture until precipitation is complete. The crude product is collected by filtration, washed with 2-propanol and dried in vacuo at 40 C. for 14 hours. Rapid crystallization from warm Q-propanol containing a slight excess of hydrogen chloride gives the intermediate N-(2-diethylaminoethyl)- N (4 amino-l-naphthyl) formamide, dihydrochloride, 1 /2 hydrate, as a lavender solid, M.P. 140 C. (dec.), of formula,

Subsequently, a cooled solution of 0.386 g. (0.0056 mole) of sodium nitrite in 50 ml. of water is added to a solution of 2.0 g. (0.0056 mole) of N-(Z-diethylaminoethyl -N- (4-aminol-naphthyl -formamide, dihydrochloride in dilute hydrochloric acid. After a few minutes, the diazonium salt solution is added at -5 C. with stirring to a solution of 0.612 g. (0.0056 mole) of 2,6-diaminopyridine in 100 ml. of water and 1.2 ml. of concentrated hydrochloric acid. Stirring is continued for several minutes and the reaction mixture is made alkaline with sodium hydroxide solution. The red solid, which exhibits a green iridescence, is collected by filtration and dried in vacuo. This is the desired intermediate, N-[4-(2,6-diamino-3- pyridylazo)-1-naphthyl]-N-(2-diethylaminoethyl) formamide, of formula,

The intermediate N- [4-(2,6-diamino-3-pyridylazo)-1- naphthyl -N- 2-diethylaminoethyl) -formamide is allowed to stand at room temperature for 18 hours in ethanolic hydrogen chloride. The mixture is concentrated and made alkaline with aqueous sodium hydroxide. The resulting maroon solid is collected by filtration, washed thoroughly with water, and crystallized from a mixture of dimethylformamide and 2-propanol. The black crystals thus obtained, M.P. 234 C. (dec.), are the desired 2,6-diamino- 3 [4 (2-diethylaminoethylamino)-1-naphthylazo]-pyridine, monohydrochloride and are identical with the material obtained by the hydrolysis of N-[4-(2,6-diamino-3- pyridylazo) 1 naphthyl]-N-(Z-diethylaminoethyD-a,a,atrifiuoroacetamide.

Example 3 To a solution of 9.5 g. (0.084 mole) of S-aminoindazole in 200 ml. of ice water and 20 ml. of concentrated hydrochloric acid is cautiously added with stirring 5.8 g. (0.084 mole) of sodium nitrite in 100 ml. of cold water. The mixture is maintained at 0 C. during the addition. When the addition is complete, the diazonium salt mixture is stirred at 0 C. for minutes and poured slowly with stirring into a solution of 27.5 g. (0.084 mole) of 1,1-diisopropyl-4-methyl 7 (l-naphthyl) diethylenetriamine in 250 ml. of water and 17.5 ml. of concentrated hydrochloric acid. Stirring is continued for 2 hours at 0 C. and the mixture is allowed to stand at room temperature for 14 hours. The reaction mixture is made strongly alkaline with 10% aqueous sodium hydroxide solution and the orange-red dye is collected by filtration, washed thoroughly with water and dried in vacuo at 40 C. for 18 hours. This is the desired 5-{4-{2-[(2-diis0propylaminoethyl)-methylamino] ethylamino} 1 naphthylazo}- indazole, of formula,

orange crystals, M.P. 107l09 C.

Utilizing the preparative methods described under Examples 1 through herein, the following related compounds can be prepared, starting from equivalent quantities of the appropriate aminoindazole and l-(dialkylaminoalkylamino -naphthalene:

5-[4-(2-dimethylaminoethylamino) -1-naphthylazo] indazole 6-{4- 3- 4-methoxypiperidino -propylamino] lnaphthylazo}-indazole 7- [4- 2-diethylaminoethylamino l-naphthylazo] indazole 6-{4 [Z-(butylmethylamino) -ethylamino] -1-naphthylazo}- 2-methylind azole 5 [4- 2-diethylaminoethylamin0 l-naphthylazo indazole 5-{6-bromo-4- 3-diethylamino-2,2-dimethylpropylamino) 1-naphthylazo}-indazole 7- [4- 2-diethylaminoethylamino) l-naphthylazo -4- indazolesulfonic acid 6- [4-( 2-diethylaminoethylamino) -6-nitro-1-naphthylazo] indazole 6-amino-7- [4- 2-diethylaminoethylamino) l -naphthylazo] lH-indazole 6- [4- (4-diethylaminocyclohexylamino 1 -naphthylazo] lH-indazole 4-{ 4- 2- allylethylamino -ethylarnino] 1 -naphthylazo}- S-amino- 1 H-ind azole 5-{4-[2-(4-methyl-1-piperazinyl) -ethylamino]-1-naphthylazo}-1H-indazole 1,1-diisopropyl-4-methyl-7 (l-naphthyl) diethylenetriamine, employed as a starting material in the above preparation, is readily prepared according to the following procedures: a solution of 1.1 kg. (25 moles) of ethylene oxide in 10 l. of 95% ethanol (kept at 0 C. to minimize the evaporation of ethylene oxide) is added in a slow stream over a period of 3 hours to a solution of 3.25 kg. (22.7 moles) of l-naphthylamine in 15 l. of 95 ethanol with stirring, maintaining the temperature at 0 C. during the addition. The reaction does not appear to be exothermic and no color change is noted. After the addition is complete, the reaction mixture is allowed to stand at room temperature for 16 hours and then boiled under reflux for 3 hours. The volatile materials are removed in vacuo on the steam bath and the residue distilled in high vacuo through an 8-inch Vigreux column to give N (2 hydroxyethyl) 1 naphthylamine as a colorless syrupy liquid, B.P. 157-161 C./0.25 mm., which solidifies in the receiver. A mixture of 1 kg. (5.35 moles) of N-(Z-hydroxyethyl)-1-naphthylamine and 9 l. of constant boiling hydrobromic acid (48%) is boiled under reflux for 24 hours with mechanical stirring. Reflux is adjusted so that approximately 500 ml. of the condensed hydrobromic acid-water mixture is collected during this period. Upon cooling, the desired bromide, hydrobromide which separates is collected by filtration, the filter cake is sucked dry, and the product is digested thoroughly by stirring with 3 l. of boiling 2-propanol. The occluded brown impurities dissolve and the off-white crystals are collected by filtration, washed with fresh cold 2-propanol and dried in vacuo at 50 C. for 24 to 48 hours; M.P. softening at 200 C., M.P. 208211 C.

In a 2 l. 3-necked flask is placed 166 g. (0.5 mole) of N-(2-bromoethyl)-1-naphthylamine, hydrobromide, 79 g. (0.5 mole) of N,N-diisopropyl-N'-methylethylenediamine, 138 g. (1.0 mole) of anhydrous potassium carbonate and 500 ml. of dimethylformamide. This mixture is stirred and heated at C. for 30 hours. Upon cooling, the reaction mixture is poured into 4 l. of water and the oil which separates is extracted thoroughly with ether. The combined ether extracts are dried over anhydrous potassium carbonate, the drying agent is collected by filtration, and the solvent removed in vacuo on the steam bath. The residue is distilled in vacuo through an 8-inch Vi greux column to give the desired 1,1-diisopropyl-4-methyl-7-(1- naphthyl)-diethylenetriamine as a pale yellow oil, B.P. 153-157 C./0.3 mm., n 1.5619.

Alternatively, a mixture of 166 g. (0.5 mole) of N-(2- bromoethyl)-1-naphthylamine, hydrobromine, 79 g. (0.5 mole) of N,N-diisopropyl-N'-methylethylenediarnine, 138 g. (1.0 mole) of anhydrous potassium carbonate and 500 ml. of toluene is stirred and boiled under reflux for 30 hours.- Upon cooling, 1 l. of 10% aqueous sodium hydroxide solution is added and the mixture is stirred until two distinct layers separate. The aqueous layer is siphoned off and extracted with 100 ml. of fresh toluene. The combined toluene extracts are dried over anhydrous potassium carbonate, the drying agent is collected by filtration and the solvent evaporated in vacuo by means of a rotary evaporator. Distillation of the residue in vacuo through an 8-inch Vigreux column gives the desired naphthylamine as a yellow oil, B.P. 149-151 C./ 0.2 mm., n 1.5613.

Xylene also serves as an excellent solvent. For example, a mixture of 118 g. (0.36 mole) of N-(2-brom0- ethyl) 1 -naphthylamine, hydrobromide, 126 g. (0.80 mole) of N,N-diisopropyl-N-methyl-ethylenediamine, and 500 ml. of xylene is stirred and boiled under reflux for 30 hours. Upon cooling, 1 l. of 10% aqueous sodium hydroxide solution is added and the mixture is stirred until the two layers separate. The aqueous layer is separated and extracted with 200 ml. of benzene. The combined benzene-xylene layers are dried over anhydrous potassium carbonate and the solvent removed in vacuo. Distillation of the residue in vacuo through an 8-inch Vigreux column gives the desired amine as a yellow oil, B.P. 153-l56 C./0.3 mm., n 1.5621.

The other intermediate l- (dialkylaminoalkylamino)- naphthalenes employed herein can be prepared according to the procedures described under Examples 1 through 15.

Example 4 A solution of 4.4 g. (0.062 mole) of sodium nitrite in 40 ml. of water is cooled to C. and is slowly added to a solution of 12.7 g. (0.062 mole) of 8-amino-5,6-dimethoxyquinoline in 200 ml. of 50% ethanol and 17 ml. of concentrated hydrochloric acid, maintaining the temperature at 0 C. This diazonium solution is subsequently added to a solution of 17.5 g. (0.62 mole) of N,N-diethyl- 2,Z-dimethyl-N-1-naphthyl-1,3-propanediamine in 200 ml. of 95% ethanol which has been made strongly acidic to Congo red with concentrated hydrochloric acid. The mixture is stirred for 2 hours at 0 C. and 18 hours at room temperature. The crude hydrochloride is collected by filtration and crystallized from isopropanol. The desired 8-[4-(3-diethylamino 2,2-dimethylpropylamino)-lnaphthylazo] 5,6-dimethoxyquinoline, trihydrochloride, of formula,

i 00113 .SHGl

contains 1 /2 moles of water of hydration and melts at l66-l70 C.

In like manner, the following related compounds can be prepared, starting from the appropriate l-(dialkylaminoalkylamino)-naphthalene and aminoquinoline: 2-{8-{4-[2-(isopropylmethylamino)-ethylamino]-1-naphthylazo}quinolyloxy}-ethanol, hydrochloride 5- [4-( Z-diethylaminoethylamino l-naphthylazo] -8-methylquinoline, hydrochloride 1-{2- [4-( 6-quinolylazo) 1 -naphthylamino] -ethyl}-3 -pyrrolidinol, hydrochloride 3-diethylamino3-[4-(6-methoxy-8-quinolylazo)-1-naphthylamino] -l l ethylimino -di-2-propanol, hydrochloride 5-[4-(2-diethylaminoethylamino)-1-naphthylazo]-7-(diethylaminomethyl)-8-quinolinol, hydrochloride 7 -chloro-4- 4-diethylaminol -methylbutylamino) -8-{4- [2- (ethylmethylamino)-ethylamino]-1-naphthylazo}- quinoline, hydrochloride a-Diethylamino-4-{5-{4-[Z-(diisopropylamino)-ethylamino] 1-naphthylazo}-2-quinolylamino}-o-cresol, hydrochloride a-Diethylamino-4-{8-[4-(2-diethylaminoethylamino)-1- naphthylazo]-4-quinolylamino}-o-cresol, hydrochloride N,N diethyl-2,2-dimethyl-N'-l-naphthyl-l,3-propanediarnine, employed as a starting material in the above procedure, can be prepared as follows: a mixture of 157 g. (1.0 mole) of fl-diethylaminopivaldehyde, 143 g. (1.0 mole) of l-naphthylamine, l g. of p-toluenesulfonic acid and 400 ml. of benzene is boiled under reflux for 8 hours. The water which separates is removed through a Dean-Stark water trap. The benzene is removed in vacuo on the steam bath, the residue is dissolved in 300 ml. of methanol, and 5 g. of 20% palladium on charcoal catalyst is added. The resulting mixture is hydrogenated in a steel bomb at room temperature under an initial hydrogen pressure of 52 p.s.i.g. When hydrogenation is complete, the solvent is removed in vacuo on the steam bath and the residue is made strongly alkaline with 10% aqueous sodium hydroxide solution. The oil which separates is extracted with benzene, the combined benzene extracts are dried over anhydrous potassium carbonate and the benzene is removed in vacuo. The residue is distilled in vacuo through a l0-inch Vigreux column to give the desired N,N diethyl-2,2-dimethyl-N'-1-naphthyl-1,3-propanediamine as a pale yellow oil, B.P. 161 C./ 1.0 mm., n 1.5790.

The other intermediate 1-(dialkylaminoalkylamino)- naphthalenes employed in the above example are prepared according to the procedures described under Examples 1 through 15 herein.

Example 5 A mixture of 4.4 g. (0.01 mole) of N-(2-bromoethyl)- 4-(3-dibenzofuranylazo)-l-naphthylamine and 50 ml. of piperidine is heated on the steam bath for one hour. The red solution is poured into 1 l. of water and the product which precipitates is collected by filtration, washed thoroughly with water, and dried in vacuo at 55 C. for 18 hours. Crystallization from acetone gives the desired 1-{2-[4-(3-dibenzofuranylazo) 1 naphthylamino]-eth yl}-piperidine, of formula,

as glistening red crystals, M.P. 164-165 C.

Alternatively, N-(Z-chloroethyl) 4 (3-dibenzofuranylazo)-1-naphthylarnine, M.P. -171 C., can be substituted for N-(2-bromoethyl)-4-(S-dibenzofuranylazo)-1- naphthylamine in the above procedure.

Utilizing the preparative methods described under Examples 1 through 15 herein, the following related compounds can be prepared, starting from the appropriate furan and l-naphthylamine precursors:

N- [4- 3 dibenzofuranylazo) -1-naphthyl] -N,N-diethylethylenediamine N- 4-(2-dibenzofuranylazo) -1-naphthyl] -N,N-diethylethylenediamine 5- [4-(Z-diethylaminoethylamino) -1-naphthylazo] -2-furancarbamic acid, ethyl ester 5- [4- (Z-diethylaminoethylamino) -1-naphthylazo] -2-benzofurancarboxylic acid N 4- 2-bromo-3 -dibenzofuranylazo) -6-chloro-1-naphthyl -N-isopropyl-N-methylethylenediamine 1-{2- [4- 6,7,8 ,9-tetrahydro-3-dibenzofuranylazo) l-naphthylamino]-ethyl}-1-pyrrolidine N [4-( 3 -dibenzofuranylazo) -l -naphthyl] -N,N-diethyl-2- methyl-1,3 -propanediamine N'- [4-( 8-acetyl-3 -dibenzofuranylazo) -7-methoxy-1-naphthyl] -N,N-diethylethylenediamine 7- [4- 3 -dibenzofuranylazo) -1-naphthyl] -1,1,4-triethyldiethylenetriamine 3 -[4- (3 -piperidinopropylamino)-1-naphthylazo]-2-dibenzofuranol N [4- (3 -dibenzofuranylazo)-1-naphthyl] -N,N-diethyl-1,

4-pentanediamine 4-( 3-dibenzofuranylazo)-N-{[ l-(diethylaminoethyl) -cyclohexyl -methyl}-1-naphthylamine N-(Z-bromoethyl)-4-(3-dibenzofuranylazo) 1 naphthylumine, employed as a starting material in the above procedure, is prepared as follows: a suspension of 18.3 g. (0.1 mole) of 3-aminodibenzofuran in 1 l. of water containing 35 ml. (0.3 mole) of 48% aqueous hydrogen bromide is cooled to C. and treated slowly with a solution of 6.9 g. (0.1 mole) of sodium nitrite in 50 ml. of water. maintaining the temperature at O to C. The resulting yellow suspension is stirred at 0 C. for onehalf hour and is then poured with vigorous stirring into a solution of 33.1 g. (0.1 mole) of N-(Z-bromoethyD-lnaphthylamine, hydrobrornide in 300 ml. of water. The thick purple suspension thus obtained is stirred for 2 hours at room temperature and the solid collected by filtration and dried in vacuo at 55 C. for 18 hours. The hydrobromide salt is converted to the base by grinding with concentrated sodium hydroxide solution and acetone and the base is crystallized from chloroform. This is the desired intermediate, N-(2-bromoethyl)-4-(3-dibenzofuranylazo)-1-naphthylamine, M.P. 157158 C.

The other intermediate l-naphthylamines employed herein can be prepared according to the procedures described under Examples 1 through 15.

Example 6 I To a solution of 9.3 g. (0.1 mole) of 3-aminopyridine in 250 ml. of water and 35 ml. of concentrated hydrochloric acid is slowly added at 0 C. with stirring a solution of 6.9 g. (0.1 mole) of sodium nitrite in 200 ml. of water. Upon completion of the diazotization, the diazonium salt solution is added at 0 to 3 C. to a solution of 27.2 g. (0.1 mole) of 1-diethylamino-3-(l-naphthylamino)-2-propanol in 1 l. of water containing 17 ml. of concentrated hydrochloric acid and 300 ml. of 95% ethanol. A deep red solution forms immediately. After 3 hours, the reaction mixture is made strongly alkaline with sodium hydroxide solution and the organic layer which separates is extracted with chloroform. The combined chloroform extracts are washed thoroughly with water and dried over anhydrous sodium sulfate. The drying agent is collected by filtration, the chloroform is evaporated in vacuo, and the residue dissolved in ether and treated with anhydrous hydrogen chloride. The purple hydrochloride which separates is collected by filtration and crystallized from an ethanol-ether mixture. After drying in vacuo for 48 hours at 40 C., the sample is allowed to equilibrate in the air. The red-brown solid melts at 154-157 C., and is the desired 1-diethylaminol-diethylamino-3-(1-naphthylamino)-2 propanol, B.P. 175178 C./0.5 mm., employed as an intermediate in the above procedure, is prepared from l-naphthol and 3- amino-1-diethylamino-2-propanol according to the method described in Example 8 herein for the synthesis of 1- (3-dimethylaminopropylamino)-naphthalene.

Alternatively, the desired azo compound can be prepared in the following manner: a solution of 12.9 g. (0.1 mole) of N,N-diethylepihydrinamine in ml. of ethanol is added with stirring to a solution of 24.8 g. (0.1 mole) of 3-(4-amino-1-naphthylazo)-pyridine in 200 ml. of ethanol and the mixture is boiled under reflux for 24 hours. The solvent is removed in vacuo and the residue is purified as described above. The desired l-diethylamino-3-[4-(3-pyridylazo)-1-naphthylamirio]-2 propanol trihydrochloride hydrate thus obtained melts at 153155 C. The intermediate 3-(4-amino-1-naphthylazo) pyridine, M.P. 185-l87 C., is prepared from l-naphthylamine and diazotized 3-aminopyridine according to the procedure described under Example 1 herein.

1-diethylarnino-3- [4-( 3-pyridylazo) -l naphthylamino] 2-propanol trihydrochloride can also be obtained by the following procedure: a mixture of 37.7 g. (0.1 mole) of.

1-chloro-3-[4-(3-pyridylazo)-1-naphthylamino] 2 propanol hydrochloride and 300 g. of diethylamine is placed in a bomb and heated at C. for 12 hours. The bomb is allowed to cool, is carefully vented and the reaction mixture poured into 2 1. of 10% aqueous sodium hydroxide solution. This mixture is worked up as indicated above to give the desired 1-diethylamino-3-[4-(3-pyridylazo)-1- naphthylamino]-2-propanol, trihydrochloride, monohydrate, M.P. 155157 C.

The intermediate 1-chl0ro-3-[4-(3-pyridylazo)-l-naphthylamino]-2-propanol, hydrochloride, is prepared by coupling diazotized 3-aminopyridine into 1-chloro-3-(1-naphthylamino)-2-propanol according to the procedure outlined in Example 1 above for the preparation of 5-[4-(2- diethylaminoethylamino -1-naphthylazo]-uracil.

The following related compounds can be prepared using similar methods, starting from the appropriate aminopyridine and l-naphthylamine compounds:

1-diethylamino-2-methyl-3-[4-(3-pyridylazo)-1- naphthylamino] -2-propanol, sulfate 2-{eth yl{2- [4- 3-pyridylazo -1-naphthylamino] ethyl}-arnino}-ethanol, diphosphate 5- [4- (Z-diethylaminoethylamino) -7-methoxy-1- naphthylazo]-2-phenoxypyridine, trihydrochloride 1-{2-{2- [4-(3-pyridylazo) -1-naphthylamino] -ethoxy}- ethyl}-piperidine, salt with 4,4'-methylenebis[3-hydroxy-2-naphthoic acid] 3-{4-{2- [bis Z-ethoxyethyl -amino] -ethylamino}- 1-naphthylazo}-pyridine, cholate 3-[4-(Z-diethylaminoethylamino)-7-phenyl-lnaphthylazo]-pyridine, malonate 4-{4-{5-[4-(Z-diethylaminoethylamino)-1-naphthylazo]- 2-pyridylamino} butyl}-morpholine 5- [4- (Z-dicyclohexylaminoethylamino) -1-naphthylazo] 2-picoline, disalicylate The intermediate l-naphthylamine compounds can be prepared according to the procedures outlined above to- 17 gether with those described under Examples 1 through 15 herein.

Example 7 Utilizing the preparative methods described under Examples 1 through 15 herein, the following related compounds can be prepared starting from the appropriate 1- naphthylamine compound and amino or hydroxybenzimidazole or indazole:

5 (or 6) -[4-(2-diethylaminoethylamino)-1- naphthyl azo -benzimidazole 5-1'4-(Z-diethylaminoethylamino)-1-naphthylazo]- 2-benzimidazolinethione 5- [4- S-diethylaminol-methylpentylamino) -1- naphthylazo l H-indazole 5 6-chloro-4- 2- (ethylmethylamino) -ethylamino] 1-naphthylazo}-1,3-dimethyl-2-benzimidazolinone 5 (or 6 -{4-{2- [4- (2-hydroxyethyl )-1-piperazinyl] ethylamino}-1-naphthylazo}-2-benzimidazolecarboxylic acid a-methyl-a- [4-( 1-phenyl-5-benzimidazolylazo) -1-naphthylaminomethyl] -1-piperidine-ethano1 8- 5 (or 6) -benzimidazolylazo)-5-(2-diethylaminoethylamino -2-naphthalenesulfonic acid 5- L 4- (3-dimethylamino-2-ethoxypropylamino) -1- naphthylazo]-2-methyl-1H-naphth-[1,2]-imidazole 7 (or 4) -{4-[ 3-(diallylamino) -propylamino] -1- naphthylazo} -2-methyl 5 (or 6) benzimidazolesulfonic acid 6 (or 5 [4- Z-diethylaminoethylamino) -1- naphthylazo] -2-methy1-5 -benzimidazoll (or 6) -{4-{2- [ethyl (Z-diisopropylaminoethyl amino] -ethylamino}-1-naphthylazo}-benzimidazole 5 (or 6 -{4- 2- Z-diethylaminoethoxy) -ethylamino] l-n aphthyl azo}-benzimid azole The starting material, 4-[3-( l-naphthylamino)-propyl]- morpholine, can be prepared as follows: a mixture of 86.4 g. (0.6 mole) of l-naphthol, 102.8 g. (0.714 mole) of 4-(l-aminopropyl)-morpholine, 93.6 g. (0.9 mole) of sodium bisulfite and 600 ml. of water is agitated in a pressure vessel at 150 C. for 8 hours. The reaction mixture is removed from the reactor and made alkaline with sodium hydroxide solution. The product is collected by filtration and crystallized from aqueous ethanol to give the desired 4-[3-(l-naphthylamino)-propyl]-morpholine as colorless crystals, M.P. 8283.5 C.

The other intermediate l-naphthylamine compounds are prepared according to the procedures described under Examples 1 through 15 herein.

Example 8 S-aminoisoquinoline (14.4 g., 0.1 mole) is diazotized and coupled with 22.8 g. (0.1 mole) of l-(3-dimethylaminopropylamino)-naphthalene according to the procedure outlined under Example 1 herein. Crystallization of the crude dye from 2-propanol gives the desired 5- 18 [4-(3-dimethylaminopropylamino)-l-naphthylazo] isoquinoline, of formula,

Utilizing the preparative methods outlined under Examples 1 through 15 herein, the following related compounds can be prepared starting from the appropriate 1- naphthylamine compound and amino or hydroxyisoquinoline:

4-[4-(2-diethylaminoethylamino) -1-naphthylazo] isoquinoline 5- [4-(Z-diethylaminoethylamino) -1-naphthylazo] isoquinoline 7-{4- 2,2-dimethyl-3-( l-pyrrolidinyl -propylamino] 1-naphthylazo}-3-ethylisocarbostyril 6- [4- (2-diethylaminoethylamin0) -1-naphthylazo]- isoquinoline 8- 3- 2,2-dimethylpiperidino) -propylamino] -5- (6- isoquinolylazo)-2-naphthoic acid 5-amino-8-[4-(2-diethylaminoethylamino) -1- naphthylazo] isoquinoline 1- Z-dimethylaminoethoxy) -3-ethyl-7-{4- 2- (isopropylmethylamino) -ethylamino] -1-naphthylazo}- isoquinoline 4-{4- 5- (dimethylaminomethyl -tetrahydrofurfurylamino l -naphthylazo}-isoquinoline 1-{3- 6-chloro-4- (7-isoquinolylazo) -1-naphthylamino] 2,2-dimethylpropyl}-4-methylpiperazine- 8- [4-(2-diisopropylaminoethylamino) -1- naphthylazo] -5-isoquinolinol 8- [4-(2-diethylaminoethylamino l-naphthylazo1- 5- 3-diethylaminopropylamino -isoquinoline 4-[4-(Z-diethylaminoethylamino)-1-naphthylazo]- 3-hydroxy-2-methylisocarbostyril The starting material, 1-(3 dimethylaminopropylamino)-naphthalene, can be prepared as follows: a mixture of 28.8 g. (0.2 mole) of l-naphthol, 40.4 g. (0.4 mole) of 3-dimethylaminopropylamine and 31.2 g. (0.3 mole) of sodium bisulfite in 250 ml. of water is shaken in a steel bomb at 150 C. for 8 hours. The mixture is rinsed from the bomb with water, made strongly alkaline with sodium hydroxide solution and extracted thoroughly with ether. The ether extracts are dried over anhydrous sodium sulfate, the ether removed in vacuo, and the residue distilled in vacuo through a 6-inch Vigreux column to give the desired 1-(3-dimethylaminopropylamino)-naphthalene as a yellow oil, B.P. 184-185 C./2.5 mm., n 1.6054.

The other intermediate l-naphthylamine compounds are prepared according to the procedures described under Examples 1 through 15 herein.

M.P. 158-160 C.

Example 9 N (2-diethylaminoethyl)-N-(4-amino-1-naphthyl)-trifluoroacetamide, monohydrochloride (9.75 g., 0.025 mole) is diazotized according to the procedure described under Example 2 herein. To this cold diazonium salt solution is then added g. of ice and a cold solution of 4.0 g. (0.027 mole) of 8-hydroxyquinoline in 100 ml. of water, 8.4 ml. (0.050 mole) of 6 N aqueous sodium hydroxide and 2.03 g. (0.025 mole) of sodium acetate. A reddishbrown precipitate forms immediately giving a thick suspension. The reaction mixture is stirred at 0-13 C. for

2 hours, and the intermediate trifluoroacetamide, of formula,

is collected by filtration, washed with water and dried in vacuo at 40 C. for 18 hours. The crude trifluoroacetamide is crystallized from 2-propanol, MP. 15 8-160 C.

The N (Z-diethylarninoethyl)-2,2,2-trifluoro-N-[4-(8- hydroxy-S-quinolylazo)-l-naphthyl]-acetamide (8.5 g.) is suspended in 75 ml. of methanol and treated with 25 ml. of a 2 N sodium hydroxide solution in methanol together with ml. of water. After stirring at room temperature for 44 hours, the residue is diluted with 150 ml. of water, excess Dry Ice is added, and the reaction mixture is concentrated in vacuo to a volume of 150 ml. The red dye that precipitates is the desired 5-[4-(2-diethylaminoethylamino)-1-naphthylazo]-8-quinolinol, of formula,

NH(CH2)2N(C2 6)l Crystallization from a dimethylformamide-water mixture gives reddish brown crystals, M.P. 161-163 C.

By similar procedures, the following related compounds can be prepared, starting from the appropriate N-(dialkylaminoalkyl) N-(4-amino-1-naphthyl)-trifluoroacetamide and hydroxyquinoline via the N-[4-(quinolylaz0)-1-naphthyl] N (dialkylaminoalkylamino) a,a,a-trifiuoroacetamides:

5 [4 (3 piperidinopropylamino) 1 naphthylazo] -6- quinolinol 3 [4 (2 diethylaminoethylamino) '1 naphthylazo]- 2,4-quinolinediol 7 [4 (3 diethylaminopropylamino)-7-sulfo-1-naphthylazo] -8-'hydroxy-S-quinolinesulfonic acid 5 [4 (2 diethylaminoethylamino) 1 naphthylazo]- a-(5-ethyl-2-quinuclidinyl)-6-hydroxy-4-quinolinemethanol 8 hydroxy 5 {4-[3-(2-morpholinoethylthio)-propylamino]-1-naphthylazo}-7-quinolinesulfonic acid 5 {4 [2-(cyclohexylmethylamino)-ethylamino]-l-naphthylazo}-4-methyl-2,6-quinolinediol 5 [4 (2 diethylaminoethylamino)-1-naphthylazo]-7- (dimethylaminomethyl) -8-quino1inol 5 chloro 7 [4-(4-diethylamino-1-methylbutylamino)- l-naphthylazo] -8-quinolinol The intermediate N-(4-quinolylazo-l-naphthyl)-N-(dialkylaminoalkyl) a,a,a-trifluoroacetamides are prepared from the appropriate hydroxyquinoline and N-dialkylaminoalkyl N (4-amino-l-naphthyl)-a,a,a-trifluoroacetamide compounds in accordance with the method described above for the preparation of N-(2-diethylaminoethyD-2, 2,2 trifluoro N-[4-(S-hydroxy-S-quinolylazo)-1-naphthylJ-acetamide.

Example 10 S-amino-Z,3-dimethylquinoxaline (17.3 g., 0.1 mole) is diazotized and coupled into 30.3 g. (0.1 mole) of N-[2- (Z-diethylaminoethylthio) -ethyl] -1-naphthylamine accord- 20 ing to the procedure described under Example 1 herein. The red dye thus obtained is the desired 6-{4-[2-(2-diethylaminoethylthio) ethylamino] 1 naphthylazo} 2,3-d1- methylquinoxaline, of formula NH(CH2)2S 2)2N( 2 s):

Utilizing the preparative methods outlined under Examples 1 through 15 herein, the following related compounds can be prepared starting from the appropriate 1 naphthylamine compound and aminoquinoxaline or aminoquinazoline 6 [4 (2 diethylaminoethylamino) l naphthylazo]- 2,3-dimethylquinoxaline 1 {2 [4 (6 methoxy-7-quinazolinylazo)-1-naphthylamino] -ethyl}-3-piperidinol 6 [4 (2,2-dimethyl-3-piperidinopropylamino)-1-naphthylazo] -quinoxaline 6 {4 [2 (allylethylamino)-ethylamino]-1-naphthylazo}-quinazoline 5 {4 [2 (cyclohexylmethylamino) -ethylamino] 1- naphthylazo}-7-methoxyquinoxaline 5 {4 {2 [4 (2 piperidinoethyl)-piperidino]-ethylamino}-1-naphthylazo}-2,3-quinoxalinediol 6 [4 (2 diethylaminoethylamino)-l-naphthylazo]-2,3-

diphenylquinoxaline 7 [4 (2 dimethylaminocyclohexylamino)-l-naphthylazo] -quinazoline 6 [4 (2 dimethylaminoethylamino)-1-naphthylazo]-4- ethyl-3,4-dihydro-2 1H) -quinoxaline 5 {4 {2 [bis( 2 diethylaminoethyl)-amino]-ethylamino}-1-naphthylazo}-quiuazoline 5 {4 [2 (hexahydro-l-azepinyl)-ethylamino]-1-naphthylazo}-7-methoxyquinoxaline a {[4 (2 quinoxalinylazo)-1-naphthylamino] -methyl}- l-piperidineethanol N [2 (2 diethylaminoethylthio)-ethyl]-1-naphthylamine, employed as a starting material in the above procedure, is prepared from 1-(2-bromoethylamino)-naphthalene and 2-diethylaminoethanethiol according to the following method: 33.9 g. (0.2 mole) of 2-diethylaminoethanethiol hydrochloride is suspended in ammonia and extracted with toluene. To this dried toluene solution is then added a solution of 12 g. of sodium methoxide in 40 ml. of methanol and the mixture is stirred at room temperature for 2 hours. A toluene solution of 1-(2-bromoethylamino)- naphthalene, prepared by suspending 66.2 g. (0.2 mole) of the hydrobromide in concentrated ammonium hydroxide and extracting with toluene, is then added and the mixture boiled under reflux for 18 hours. Upon cooling, the sodium bromide which separates is collected by filtration and the filtrate is washed twice with water, dried over anhydrous potassium carbonate and evaporated in vacuo on the steam bath. The residue is distilled in vacuo through an 8-inch Vigreux column to give the desired N [2 (2 diethylaminoethylthio) ethylJ-l-naphthylamine as a yellow oil, B.P. 164-l65 C./0.1 mm., n 1.6015.

The other intermediate l-naphthylamine compounds are prepared according to the procedures described under Examples 1 through 15 herein.

Example 11 A solution of 5.0 g. (0.05 mole) of 2-aminothiazole in 250 ml. of 50% sulfuric acid is cooled to 10 C., and nitrosyl sulfuric acid (3.5 g. of sodium nitrite in 35 ml. of concentrated sulfuric acid) is slowly added, keeping 21 the temperature between 10 and C. The resulting light brown solution is stirred for 30 minutes, then added to a solution of 12.7 g. (0.05 mole) of 1-[2-(l-naphthylamino)-ethyl]-piperidine in 250 ml. of sulfuric acid. A dark red solution formed. After stirring for 2 hours at 0 to l0 C., l l. of water is added yielding a purple solution. Stirring is continued for 1 hour and the mixture is made alkaline with sodium hydroxide solution with cooling. The mixture is stirred for 24 hours and the sticky dye collected by filtration and washed with copious amounts of water to remove inorganic salts. The product is dissolved in chloroform; the chloroform solution is washed well with water, dried over anhydrous potassium carbonate, and the solvent removed in vacuo. The viscous residue is dissolved in acetone and precipitated by pouring the acetone solution into water. Upon heating the suspension, a crystalline solid separates which is collected by filtration and dried in vacuo at 45 C. Crystallization from an ethanol-water mixture gives the desired 1{2-[4-(2-thiazolylazo)1 naphthylamino]-ethyl}-piperidine, of formula,

NH (0 H2) 2N as emerald green, shimmering crystals, M.P. 135-137 C.

Utilizing the preparative methods outlined under Examples 1 through herein, the following related compounds can be prepared starting from the appropriate 1-naphthylamine compound and aminothiazole:

2- [4-(Z-diethylaminoethylamino) -1-naphthylazo]- thiazole 2-{4-[2-(isopropylmethylamino)-ethylamino]-1- naphthylazo}-5-nitrothiazole 2-{4-{2- (Z-diethylaminoethyl) ethylamino] -ethylamino}- 1-naphthylazo}-4-methylthiazole 2-[4-(6-diethylaminohexylamino) -1-naphthylazo] thiazole 2- [4- 3-dimethylamino-Z,Z-dimethylpropylamino) -1- naphthylazo-] -4-phenylthiazole 4-(2-dimethylaminoethyl) -1-{3-[4-(2-thiazolylazo)- lnaphthylamino] -propyl}-piperidine 2- [4-(2-diethylaminoethylamino)-1-naphthylazo]-4- (trifluoromethyl -thiazole 2- [4-(Z-diethylaminoethylamino) -5-methoxy-1- naphthylazo] -thiazole 2- [4-(Z-diethylarninoethylamino) -1-naphthylazo] -4- ethylsulfonyl-S-nitrothiazole 2- [4- 2-dihexylaminoethylamino) -1-naphthylazo] thiazole 2,2'-{2- [4- 2-thiazolylazo) l-naphthylamino] ethylimino}-diethanol l-methyl-4-{2- [4-(2-thiazolylazo) -1-naphthylamino]- ethyl}-piperazine The starting material, 1-[2-(1-naphthylamino)-ethyl]- piperidine, can be prepared as follows: a mixture of 19 g. (0.057 mole) of N-(Z-bromoethyl)-1-naphthylamine, hydrobromide and 100 ml. of piperidine is boiled under retlux for 20 hours and cooled; 100 ml. of 10% sodium hydroxide solution is added, and the mixture extracted with ether. The combined ether extracts are washed thoroughly with water, dried over anhydrous potassium carbonate, and the ether removed on the steam bath. "The residue is distilled in vacuo through an 8-inch Vigreux column to give the desired 1-[2-(1-naphthylamino)-ethyl]-piperidine as a pale yellow oil with a purple fluorescence, B.P. l68170/0.5 mm., n 1.6088.

The other intermediate 1-(dialkylaminoalkylamino)- naphthalene compounds employed herein are prepared according to the procedures described under Examples 1 through 15.

Example 12 3-aminoquinoline (14.4 g., 0.1 mole) is diazotized and coupled into 24.2 g. (0.1 mole) of 1-(2-diethylaminoethylamino)-naphthalene according to the procedure outlined under Example 1 herein for the preparation of 5- [4 (2 diethylaminoethylamino)-l-naphthylazo]-uracil. Crystallization of the crude dye from 2-propanol (decolorizing charcoal) gives the desired 3-[4-(2-diethylaminoethylamino)-1-naphthylazo]-quinoline, of formula,

as red crystals, M.P. l24125 C.

Alternatively, the desired 3-[4-(2-diethylaminoethylamino)-1-naphthylazo]-quinoline and other related compounds can be prepared by alkylating the appropriate (4- aminod-naphthylazo)-heterocyclic compound with a suitable dialkylaminoalkyl halide. Thus, 3- [4-(2-diethylaminoethylamino)-1-naphthylazo]-quinoline is prepared according to the following procedure: to a xylene solution of 29.8 g. (0.1 mole) of 3-(4-amino-l-naphthylazo) -quinoline and 13.6 g. (0.1 mole) of 2-diethylaminoethylchloride is added 13.8 g. (0.1 mole) of anhydrous potassium carbonate and the resulting mixture is boiled under reflux for 24 hours. The cooled reaction mixture is washed with 50% sodium hydroxide solution and the xylene layer is separated and dried over anhydrous sodium sulfate. Volatile materials are removed in vacuo and the residue is crystallized from 2-propanol to give the desired 3-[4-(2-diethylaminoethylamino)-1-naphthylazo]-quinoline as red crystals, M.P. l24-125 C.

The intermediate 3-(4-amino-l-naphthylazo)-quinoline, M.P. 238239 C., is prepared from diazotized 3-aminoquinoline and l-naphthylamine according to the procedure described above for the coupling with I-(Z-diethylaminoethylamino)-naphthalene.

Utilizing the preparative methods described under Examples 1 through 15 herein, the following related compounds can be prepared, starting from the appropriate 1- naphthylamine and aminoquinoline precursors:

6- [4-(2-diethylaminoethylamino) -1-naphthylazo]- quinoline 1-{2- [4- 3 -quinolylazo -l-naphthylamino] -ethyl}-3- piperidinol 3- [4- 2-diethylaminoethylamino) -7-methyl-1- naphthylazo] -quinoline 3-{4-{2- [bis( 3-diethylaminopropyl) amino] -ethylamino}- 1-naphthylazo}-quinoline 2- [4-(2-diethylarninoethylamino)-1-naphthylazo]- quinoline 3-{6-ethoxy-4- [2- (isopropylmethylamino) -ethylamino] 1-naphthylazo}-quinoline 3-[4-(-diethylaminohexylamino)-1-naphthylazo]- quinoline 3-{4-[3-(hexahydro-l-azepinyl)-propylamino]-1- naphthylazo}-quinoline 8-(2-diethylaminoethylamino)-5-(3-quinolylazo)-1- naphthalenesulfonic acid 3-{4- 2-( 1-methyl-2-piperidinyl -ethyl amino] 1- naphthylazo}-quinoline 3 -{4-{ 1- (diethylaminomethyl -cyclohexylrnethyl amino}- l-naphthylazo}-quinoline 4-{2-[4-(3-quinolylazo)-1-naphthylamino]-ethyl}-I- piperazineethanol The other intermediate l-naphthylamine compounds are prepared according to the procedures described under Examples 1 through 15 herein.

Example 13 4-amino-2,3-dimethyl-l-phenyl-3-pyrazolin-5-one (10.2 g., 0.05 mole) is diazotized and coupled into 12.8 g. (0.05 mole) of 1-(2-diethylaminoethylamino)-6-methoxynaphthalene according to the procedure outlined under Example 6 herein for the preparation of l-diethylamino- 3-[4-(3-pyridylazo) 1 naphthylamino]-2-propanol, trihydrochloride. Crystallization of the crude dye from a 2-propanol-methanol mixture gives the desired 4-[4-(2- diethylaminoethylamino)-7-methoxy 1 naphthylazo]- 2,3-dimethyl-1-phenyl-3-pyrazolin-5-one, dihydrochloride, as blue crystals, of formula,

.2IICl 011 which in hydrated form melt at ZOO-202 C.

Utilizing the preparative methods described under Examples 1 through 15 herein, the following related compounds can be prepared, starting from the appropriate l-naphthylamine and pyrazole intermediates:

3-{4-{4- [2- (allylethylamino) -ethylamino] -1-naphthylazo}-3-methyl-5-ox0-2-pyrazolin-1-yl}-4-chlorobenzenesulfonic acid, hydrochloride 4-{4-[2,2-dimethyl-3-( l-pyrrolidinyl) -propylamino]-1- naphthylazo}-5-hydroxy-3 -methyll-pyrazoleethanol, dihydrochloride 4- [4- (2-diethylaminoethylamino) -1-naphthylazo] -2,3-

dimethyl- 1 -phenyl-3-pyrazolin-5-one 1-methyl-4-{2-[4-(4-pyrazolylazo)-1-naphthylamino]- ethyl}-homopiperazine 4- 7-chloro-4- (4-diethylaminol -methylbutylamino lnaphthylazo] -3 ,5 -dimethylpyrazole 4-{4- [Z-(ethylmethylamino) -ethylamino] -1-naphthylazo}-5 -hydroxyl-p-sulfopl1enyl-3-pyrazolecarboxylic acid 4- [4- 3 -dimethylamino-2,Z-dimethylpropylamino) -1- naphthylazo -2,3-dimethyl- 1 -phenyl-3 -pyrazolin-5-one 5- I' 4- 3 -diethylaminocyclohexylamino l -naphthylazo] 3 ,4-dimethyll -phenylpyrazole 4-{4-{ 2- (Z-ethoxyethyl (2-hydroxyethyl amino] -ethylamino}- l-naphthylazo}-5-hydroxy-1-p-sulfophenyl- 3-pyrazolecarboxylic acid 2, 3-climethyl-4-{4-{2- [4- Z-piperidinoethyl -piperidino] ethylamino}-l-naphthylazo}-1-phenyl-3 -pyrazolin-5- one rn-{4- 4- 2-di isopentylaminoethylamino l -naphthylazo] -5-hydroxy-3 -methyl- 1 -pyrazolyl}-benzenesulfonic acid 3 (or 5 -{4- {2- [methyl Z-piperidinoethyl) amino]-ethylamino}-1-naphthylazo}-4-pyrazolecarboxylic acid.

4- [4-( 3-diethylamino-Z-hydroxypropylamino -1-naphthylazo]-2,3-dimethyll-phenyl-3-pyrazolin-5-one 8- 3-dimethlaminopropylamino -4- 2,3-dimethyl-5-oxo- 1-phenyl-3-pyrazolin-4-ylazo) -2-naphthalenesulfonic acid 1-(2 diethylarninoethylamino)-6-methoxynaphthalene, B.P. l95196 C./2 mm., 11 1.5904, employed as a starting material for the above procedure, can be prepared from 6-methoxy-l-naphthylamine and Z-diethylaminoethylchloride hydrochloride in accordance with the method set forth under Example 1 herein for the preparation of 1-(2diethylaminoethylamino)-naphthalene. The other intermediate l-naphthylamine compounds can be prepared according to the methods outlined under Examples l through 15 herein.

Example 14 To a solution of 9.75 g. (0.025 mole) of N-(2-diethylaminoethyl)-N-(4-amino 1 naphthyl)-trifluoroacetamide, monohydrochloride, in 100 ml. of ice water and 4.5 ml. of concentrated hydrochloric acid is added 25 ml. of 1 molar sodium nitrite solution over a period of 2 minutes. The resulting red solution is stirred for 4 minutes and added in one portion to a solution of 10.51 g. (0.025 mole) of 8-(2-diisobutylaminoethylamino)-6- methoxyquinoline, dihydrochloride, monohydrate, in 100 ml. of water, 10 ml. of concentrated hydrochloric acid and 100 g. of ice. The maroon reaction mixture is stirred at 05 C. for 2 hours, 15 ml. of concentrated amonium hydroxide is added and the maroon solid which separates is collected by filtration and washed with water. Upon drying in vacuo, the crude intermediate trifluoroacetamide of formula,

melts at 50-70" C.

The above amide (16.7 g.) is dissolved in 400 ml. of methanol, 15 ml. of 6 N aqueous sodium hydroxide is added, and the mixture is stirred at 40 C. under nitrogen for 5 days. The mixture is cooled, and the deep maroon crystals which separate are collected by filtration and washed successively with cold methanol and water. Crystallization from ethanol gives the desired 5-[4-(2- diethylaminoethylamino) 1 naphthylazo] 8 (2-diiso butylaminoethylamino)-6-methoxyquinolinc, of formula,

I (if) M.P. 9294 C. (dec.).

By similar procedures, the following related compounds can be prepared, starting from the appropriate N-(dialkylaminoalkyl)-N-(4 amino-l-naphthyl)-trifiuoroacetamide and aminoquinoline via the N-[4-(quinolylazo)-1-naphthyl] N (dialkylaminoalkylamino)-a,a,atrifluoroacetamides:

2-{8-(2-diisobutylaminoethylamino -5- [4-(2-diisopropylaminoethylamino) -1-naphthylazo]-6-quinolyloxy}- ethanol 4-{3-{5- [4- (2-diethylaminoethylamino) -1-naphthylazo] 6-methoxy-S-quinolylamino}-propyl}-1-piperazineethanol 1-{2-{6-methoxy-5- [4- 3-piperidinopropylamino -1- naphthylazo -8-quinolylamino} ethyl} -4-methylpiperazme 8- (4-amino- 1 -methylbutylamino -5- [4- Z-diethylaminoethylamino 1 -n a phthylazo -'6-methoxyquinoline 5- 4- Z-diethylaminoethylamino l -naphthylazo -8- (4- diethylamino- 1 -methylbutylamino -6-methoxyquinoline 5 [4- 2-diethylaminoethylamino 1 naphthylazo] 6- ethoxy-8-[3-( l-piperazinyl)-propylamino]-quino1ine 6-methoxy-5-{4- 2- (4-methyl- 1 piperazinyl ethylamino] -1-naphthylazo}-8- [3-(4-methyl-l-piperazinyl) propylamino] quinoline 6-methoxy-8-[ l-methy1-4- (4-methyll piperazinyl butylamino 5-{4- [2-( l-pyrrolidinyl) ethylamino 1-naphthylazo}-quinoline The intermediate N (4-quinolylazo-1naphthyl)N- (dialkylaminoalkyl) a,a,a trifluoroacetamides are prepared from the appropriate aminoquinoline and N-dialkylaminoalkyl-N-(4 amino-l-naphthyl)-a,a,a-trifiuoroacetamide compounds in accordance with the method described above for the preparation of N-(Z-diethylaminoethyl)N-{4-[8-(2-diisobutylaminoethylamino) 6 methoxy-5quinolylazo]1naphthyl}2,2,2-trifluoroacetamide.

Example 15 N (2 diethylaminoethyl) N (4 amino 1- napthyl)-trifiuoroacetamide, monohydrochloride (9.75 g., 0.025 mole), is diazotized according to the procedure described under Example 2 herein. To this cold diazonium salt solution is then added 400 g. of ice, followed by the slow addition of a warm solution of 3.2 g. (0.025 mole) of barbituric acid in 4.2 ml. (0.025 mole) of 6 N aqueous sodium hydroxide, 2.1 g. (0.025 mole) of sodium bicarbonate and 200 ml. of water. The resulting golden orange suspension is stirred for 1 hour at C., a mixture of 25 ml. (0.025 mole) of 1 M sodium bicarbonate and 4.2 ml. (0.025 mole) of 6 N aqueous sodium hydroxide is added, and the mixture is allowed to warm slowly to room temperature. Stirring is continued for 48 hours and the brown gelatinous precipitate is collected by filtration. This is resuspended in water. stirred for 18 hours and treated with an excess of Dry Ice. The suspended solid is collected by filtration, washed with water and dried. Crystallization from an ethanoldimethylformamide mixture gives the desired [4 (2 diethylaminoethylamino) 1 naphthylazo]- barbituric acid, of formula,

as reddish-black crystals, M.P. 209213 C.

By similar procedures, the following related compounds can be prepared, starting from the appropriate l-(dialkylaminoalkylamino)naphthalene via the N-[4-(pyrimidylazo) 1 naphthyl] N (dialkylaminoalkylamino)- a,a,a-trifluoroacetamides:

5- 4- (Z-diethylaminoethylarnino) -1-naphthylazo] 2- thiobarbituric acid 5-{4-[2-(isopropylmethylamino)ethylamino]-1-naphthylazo}2-methyl-4,6-pyrimidinediol 2-amino-5-{4-{ 2- bis (2-ethoxyethyl amino] ethylamino}-1naphthylazo}-4,6-pyrimidinediol 5-[4-(2-diethylaminoethylamino)-1-naphthylazo]-1,3-

dimethylbarbituric acid 6-amino-5-[4-(2,2-dimethyl-3piperidinopropylamino)- l-naphthylazo uracil 5-{4-{3- [4- (3-diethylaminopropyl)-1-piperazinyl] propylamino}-1-naphthylazo}-barbituric acid 1.3-diisopropyl-5-[4-(Z-dimethylaminoethylamino)1- naphthylazo]-barbituric acid 2,6-diamino-5- [4- 3diallylaminopropylamino) l naphthylazo]4-pyrimidinol 5-{7-chloro-[4-(2diethylaminoethylamino)-l-naphthylazo]}-barbituric acid 2,6-diamino-5-[4-(Z-diethylaminoethylamino)-1- naphthylazo]-4-pyrimidino1 5-{4-['2-(1-methyl-2-piperidyl)-ethylamino]-lnaphthylazo}-barbituric acid 5-{4- [Z-(Z-diethylaminoethoxy) ethylamino] -1- naphthylazo}-barbituric acid The intermediate N [4 (pyrimidylazo) 1 naphthyll N (dialkylaminoalkylamino) oc,oz,a trifluoroacetamides are prepared in a similar manner from the appropriate pyrimidine and N-dialkylaminoalkyl-N-(4- amino-l-naphthyl)-a,a,a-trifluoroacetamide compounds.

Example 16 A solution of 9.4 g. (0.052 mole) of 6-amino-2H-l,4- benzothiazin-3(4H)-one in 50 ml. of water, 50 ml. of ethanol and 30 ml. of concentrated hydrochloric acid is cooled to 5 C. and diazotized by the addition of 3.6 g. (0.052 mole) of sodium nitrite in 20 ml. of water. After 5 minutes, the diazonium salt is added with stirring to a solution of 12.6 g. (0.052 mole) of 1-(2-diethylaminoethylamino)naphthalene in a mixture of 1 l. of water and 50 ml. of concentrated hydrochloric acid which had previously been cooled to 0 C. The resulting purple mixture is stirred for 2 hours, and the bright orange-red base precipitated by the addition of an excess of concentrated ammonium hydroxide. The crude dye is collected by filtration and thoroughly triturated with several portions of hot water. Crystallization from 2- propanol gives the desired 6-[4-(2-diethylaminoethylamino) 1 naphthylazo] 2H 1,4 benzothiazin- 3(4H)-one, of formula,

as red luminous crystals, M.P. 213214 C.

In similar manner, the following related compounds can be prepared by diazotizing the appropriate aminobenzothiazine or aminophenothiazine and coupling the diazonium compounds thus obtained with the corresponding l-naphthylamine:

6-{4-{2- [4- (Z-diethylaminoethyl piperidino] ethylamino}-1-naphthylazo}-2H-1,4-benzothiazine 7- [4-(Z-diethylaminoethylamino) 1-naphthylazo1-2- trifluoromethyl phenothiazine 6- 4-( 1methyl-4-piperidylamino)1-naphthylazo1-2H- 1,4-benzothiazin-3 (4H) one 3-{7-[4-(2-diethylaminoethylamino) 1-naphthylazo1-6- Z-dimethylaminoacetamido 2-ethyl-3-methyl-2H- 1,4-benzothiazin-4 3H) -yl}- 1 ,2-propanediol 6- [7-chloro-4- Z-diethylaminoethylamino l-naphthylazo 2H- 1 ,4-benzothiazin-3 (4H one 3- [4-(Z-diethylamino-l-methylethylamino)-1-naphthylazo]10-ethylphenothiazine 7- [4-(Z-diethylaminoethylamino) -1-naphthylazo] 6-(N- methylmethanesulfonamido) -2H-1,4-benzothiazine- 4 3H) -ethanesulfonic acid, l-oxide, monosodium salt 3-[4- (Z-diethylaminoethylamino) 1-naphthylazo] phenothiazine 10- S-dimethylaminopropyl -7-{4- 2- (isopropylmethylamino -ethylamino] -1-naphthylazo}-2- (trifluoromethyl) phenothiazine 4-{2-[4-(3,4-dihydro-3-oxo-2H-1,4-benzothiazin-6- ylazo) 1-naphthylamino] -ethyl}-1-piperazineethanol 27 10-ethyl-3-{4-[2-( l-pyrrolidinyl)-ethylamino] 1- naphthylazo}-phenothiazine, 5,5-dioxide 6- [4- 2-methyl-3-piperidinopropylamino 1-naphthylazo] -2H- 1 ,4-benzothiazin-3 (4H) -one The other intermediate l-(dialkylaminoalkylamino)- naphthalene intermediates are prepared according to the procedures described under Examples 1 through 15 herein.

Example 17 5-amino-8-quinolinol (10.0 g., 0.048 mole) is diazotized and coupled into 12.4 g. (0.048 mole) of 2-{ethyl- [2 (1 naphthylamino)-ethyl]-amino}-ethanol according to the procdure outlined under Example 3 herein for the preparation of 5-{4-{2-[(2-diisopropylaminoethyl)-methylamino}-l-naphthylazo]}-indazole. The crude dye base is dissolved in l l. of ethanol, the solution is filtered, and the desired 2-{ethyl{2 [4 (8 hydroxy-5-quinolyazo)-lnaphthylazo]-ethyl}-amino}-ethanol, dihydrochloride, of formula,

CZHB

2)2NCHaCH2OH is caused to precipitate by the addition of 50 ml. of 4 N ethanolic hydrogen chloride. The salt is collected by filtration, dried in vacuo, and allowed to equilibrate in the air. The brown hydrated solid melts at 190l92 C.

Utilizing the preparative methods outlined under Examples 1 through 15 herein, the following related cmpounds can be prepared starting from the appropriate 1- naphthylamine compound and aminoquinoline:

3 -{4- 2- -ethyl-2-methylpi peridino -ethylamino] -lnaphthylazo}-quinoline 8- [4- Z-diethylaminoethylamino) -1 -naphthylaz0] -udiethylaminornethyl -2-phenyl-4-quinolinemethanol 5-{4-{ 2- [bis (2-methoxyethyl) -amino] -ethylamino}-1- naphthylazo}-quinoline 3- [4- 2-diethylaminoethylamino -5-nitro-l-naphthylazo] -quinoline 1-{ 2- [4- 8-quinolylazo l-naphthylamino] -ethyl}- lazaspiro- [4,5] decane 2,2'-{ 3- S-phenylazo-8-quinolylazo) -1-naphthylamino] -propylamino}diethanol 2- {8- [4- 3 -diethylamino-2-ethoxypropylarnino -1- naphthylazo] -6-quinolyloxyethanol 3-{4-[2- (allylethylamino) -ethylamino]-1-naphthyl azo}-quinoline 8-{4- [5- dimethylaminomethyl )tetrahydrofurfurylamino] -1-naphthylazo}-5-nitroquinoline 3-{4- 2- (4-methyll-homopiperazinyl -ethylamino] l-naphthylazo}-quinoline 6- [4- 3-diethylamino-2-methylpropylamino) -7-methoxyl-naphthylazo] -5 ,8-diethoxy-4-methylcarbostyril 8- [4 2-diethylamino-2-methylpropylamino) l-naphthylazo] -quinoline 2-{ethyl[2-( l-naphthylamino)-ethyl] -amino} ethanol, B.P. 170l72 C./0.2 mm., n 1.6109, employed as a starting material in the above procedure, is prepared from N (2-bromoethyl)-l-naphthylamine, hydrobromide and N-ethylethanolamine according to the method described under Example 5 herein for the preparation of 1,1-diisopropyl-4-methyl-7-(1-naphthyl)-diethylenetriamine. The other intermediate 1 (dialkylarninoalkylamino) naphthalenes employed herein can be prepared from the ap- 28 I propriate l-naphthylamine or l-naphthol according to the procedures described under Examples 1 through 15.

Example 18 S-aminouracil (9.5 g., 0.075 mole) is diazotized and coupled into 21.3 g. (0.075 mole) of 1-(5-diethylaminopentylamino)-naphthalene according to the procedure outlined under Example 1 herein for the preparation of 5 [4 (2 diethylaminoethylamino) 1 naphthylazo]- uracil. Crystallization of the crude dye from a dimethylacetamide-water mixture gives the desired 5-[4-(5-diethylaminopentylamino) 1 naphthylazo] uracil, of formula,

OH N as deep red crystals, M.P. C. (dec.).

Utilizing the preparative methods described under Examples 1 through 15 herein, the following related compounds can be prepared, starting from the appropriate 1- (dialkylaminoalkylamino) naphthalene and 5 aminouracil:

5-[4-(3-diethylamino-Z-hydroxypropylarnino-l-naphthylazo]-uracil, salt with /a formula weight 4,4- methylenebis(3-hydroxy-2-naphthoic acid) 8- Z-diethylaminoethylamino -5- (2,4-dihydroxy-5- pyrimidinylazo) -2-naphthalenesulfonic acid 5-{4-{2-[ethyl(Z-hydroxyethyl)-amino]-ethylamino}- 1-naphthylazo}-uracil, cholate 5-{4-{ ldiethylaminornethyl -cyclohexylmethyl] amino}-l-naphthylazo}-uracil, 8-chlorotheophyllinate 5-[4-(S-diethylaminooctylamino)-l-naphthylazo]- uracil, phosphate 5-[4-(2-diethylaminoethylamino)-6-ethoxy-l-naphthylazo]-uracil, malonate 5-{4-[2-(3-diethylaminopropylthio)-ethylamino]-1- naphthylazo}-uracil, succinate 5-{4- [2,2-dimethyl-3-( l-pyrrolidinyl -propylamino] 1-naphthylazo}-uracil, fi-resorcylate 5- [4- (Z-diethylaminoethylamino) -7-nitro-1-naphthylazo]-uracil, citrate 5-{4-[2-(decahydro-1-quinolyl)-ethylamino]-1-naphthylazo}-uracil, salt with 4-biphenylcarboxyllc acid 5-{4- [2-(4-methyl-1-piperazinyl)-ethylamino] -1-naphthylazo}-uracil, adipate 5- [4- 2-dihexylaminoethylamino) l -naphthylazo] uracil, salicylate 5-{4- [2-( l-azaspiro [4,5] decan-l-yl -ethylamino] l-naphthylazo}-uracil, salt with 3-hydroxy-2-naphthoic acid 1 (5 diethylaminopentylamino) -naphthalene, B.P. 198-200 C./ 1.8 mm., n 1.5740, employed as a starting material for the above procedure, can be prepared from l-naphthylamine and 5-diethylaminopentylchloride hydrochloride in accordance with the method set forth under-Example 1 herein for the preparation of 1-(2-diethylaminoethylamino)-naphthalene. Other intermediate 1-(dialkylaminoalkylamino)-naphthalenes can be prepared from a l-naphthylamine or l-naphthol compound according to the procedures outlined in Examples 1 through 15 herein.

Example 19 3-aminopyridine (9.3 g., 0.1 mole) is diazotized and coupled into 24.2 g. (0.1 mole) of 1-(2-diethylaminoethylamino)-naphthalene according to the procedure outlined under Example 6 herein for the preparation of l-diethylamino-3-[4-(3-pyridylazo) 1 naphthylamino]-2- 29 propanol, trihydrochloride. The maroon solid thus obtained, M.P. 13914l C., is the desired 3-[4-(2-diethylaminoethylamino) 1 naphthylazo]-pyridine, trihydrochloride, of formula,

NH(CII2)2N(C2H5)2 containing 3 /2 moles of water of hydration.

Utilizing the preparative methods described under Examples 1 through 15 herein, the following related compounds can be prepared, starting from the appropriate 1- naphthylamine and aminopyridine precursors:

2-[4-(Z-diethylaminoethylamino) -1-naphthylazo]- pyridine, trihydrochloride 4-(2-diethylaminoethyl)-l-{2-[4-(3-pyridylazo)-1- naphthylamino] -ethyl}-piperidine 4-[4-(2-diethylaminoethylamino)-l-naphthylazo1- pyridine, trihydrochloride 3-[4-(4-diethylamino-1-methylbutylamino)-1-naphthylazo] -pyridine 3- [4 3-diethylaminocyclohexylamino) 1 -naphthylazo] pyridine 3- 4-( 6-diethylaminohexylamino) -1-naphthylazo] pyridine 3- [4-( 3-diethylamino-2,Z-dimethylpropylamino 1- naphthylazo] -pyridine l-{- [4-( 3-pyridylazo) l-naphthylamino] -pentyl}- piperidine 3- [4-( Z-dimethylaminol-methylethylamino) -1- naphthylazo] -pyridine 3-{4-{2-{ [2- 2-diethylaminoethoxy) ethyl] -ethylamino}- ethylamino}- l-naphthylazo}-pyridine 3-{4-[2-(isopropylmethylamino) -ethylamino] -1- naphthylazo}-pyridine 3-{4-[2-(hexahydro-4-methyl-1,4-diazepin-1-yD-ethylamino] -1-naphthylazo}-pyridine The other substituted l-naphthylamines employed herein are prepared according to procedures similar to those described under Examples 1 through 15.

Example 20 2-aminodibenzothiophene (4.7 g., 0.024 mole) is diazotized and coupled into 6.1 g. (0.024 mole) of N-butyl- N-methy1-N'-l-naphtlhylethylenediamine according to the procedure described under Example 1 herein. The crude red dye is washed thoroughly with cold water, dissolved in a hot methanol-acetone mixture, and poured with stirring into water containing a few drops of ammonium hydroxide. The finely divided precipitate thus obtained is coagulated by heating, collected by filtration, and crystallized from 2-propanol. This is the desired N-butyl- N -[4 (dibenzothiophene 2 ylazo) 1 naphthyl]- N-methylethylenediamine, of formula,

M.P. l20-12l C.

Utilizing preparative procedures similar to those described under Examples 1 through herein, the following related compounds can be prepared, starting from the appropriately substituted l-naphthylamine compound and hydroxy or amino dibenzothiophene or thiaraphthene:

The starting material, N-butyl-N-methyl-N'-1-naphthylenediamine, B.P. 142-144" C./0.1 mm., n 1.5800, is prepared from l-naphthylamine and Z-(butylmethylamino)-ethyl chloride, hydrochloride, according to the procedure outlined under Example 1 for the preparation of 1 (2 diethylaminoethylamino) naphthalene. The other substituted l-naphthylamines employed are prepared according to procedures similar to those outlined under Examples 1 through 15.

Example 21 S-aminouracil (6.4 g., 0.05 mole) is diazotized and coupled into 15.7 g. (0.05 mole) of 1,1,4-triethyl-7-(lnaphthyl)-diethylenetriamine according to the procedure outlined under Example 4 herein for the preparation of 8 [4 (3 diethylamino 2,2 dimethylpropylamino)- l-naphthylazo] -5,6-dimethoxyquinoline, trihydrochloride. Crystallization of the crude dye from a methanol-Z-propanol mixture gives the desired 5-{4-{2-[(Z-diethylaminoethyl) ethylamino] ethylamino} 1 naphthylazo}- uracil, trihydrochloride, of formula,

ZZl li...

as dark blue crystals, M.P. 164-167 C.

Utilizing the preparative methods described under Examples 1 through 15 herein, the following related compounds can be prepared, starting from the appropriate 1- naphthylamine and pyrimidine intermediates:

4,6-diamino-5- [4- Z-diethylaminoethylamino) -1- naphthylazo] -pyrimidine 2,4-diamino-5- [4- (Z-diethyIaminoethylamino) -1- naphthylazo]-6-ethylpyrimidine 2,4-bis( diethylamino) -5- [4-( 1 methyl-3-piperidylmethylamino -1 -naphthylazo] pyrimidine 2,4-diamino-5-{4- 2-( isopropylmethylamino) -ethylamino] -1-naphthylazo}-pyrimidine 2-amino-5-[7-chloro-4-(Z-diethylaminoethylamino) -1- naphthylazo] -4-piperidinopyrimidine 2,4,6-triamino-- {4- [2- 4-methyll-piperazinyl) -ethy1- amino] -1-naphthylazo}-pyrimidine 4-amino-5- [4-(Z-diethylaminoethylamino) -1-naphthylazo] -2-(4-piperidinobutylamino -pyrimidine 2- Z-diethylaminoethylamino) -5- [4-( Z-diethylaminoethylamino) -1-naphthylazo]-4-methoxypyrimidine 4-diethy1amino-5 -{4- [2- isopropylmethylamino) -ethylamino] -1-naphthylazo}-2- S-piperidinopentylamino) pyrimidine 4-diethylamino-2-( 4-diethylaminobutylamino) -5- [4- 2- diethylaminoethylamino)-1-naphthylazo] -pyrimidine 2-amino-4-anilino-5- [4-(Z-diethylaminoethylamino) -1- naphthylazo] -pyrimidine 4-amino-2- 4-diethylaminol-methylbutylamino) -5 [4- (4-diethylamino-1-methylbutylamino)-1-naphthylazo]- 6-methylpyrimidine 2,4-bis( 3-piperidinopropylamino) -5- [4- B-piperidinopropylamino l-naphthylazo] pyrimidine 1,1,4 triethyl 7 (1 naphthyl)-diethylenetriamine, B.P. 145-148 C./0.1 mm., n 1.5715, employed as a starting material in the above procedure, is prepared from N-(2-bromoethyl)-1-naphthylamine, hydrobromide and N,N,1 I'-triethylethylenediarnine according to the method described under Example 3 herein for the preparation of 1,1 diisopropyl 4 methyl 7 (1 naphthyl) diethylenetriamine. The other intermediate l-(dialkylaminoalkylamino)-naphthalenes employed herein can be prepared from the appropriate naphthalene compound according to the procedures described under Examples 1 through 15.

Example 22 S-amino-1,4-dihydroxyphthalazine (17.7 g., 0.1 mole 1s diazotized and coupled into 24.3 g. (0.1 mole) of l-(2 diethylaminoethylamino)-naphthalene according to the procedure outlined under Example 3 herein for the preparation of 5-{4-{2-[(2-diisopropylaminoethyl)-methylamino} 1 naphthylazo]}-indazole. Crystallization of the crude dye from a dimethylacetamide-Z-propanol mixture gives the desired 5-[4-(2-diethylaminoethylamino)-1- naphthylazo]-l,4-phthalazinediol, of formula,

as greenish-black crystals, M.P. 211-213 C.

Utilizing the preparative methods described under Examples 1 through herein, the following related compounds can be prepared, starting from the appropriate 1 -naphthylamine and aminophthalazine or aminophenazine precursors:

5-{4-{2-[2-(2-piperidinoethyl)-piperilino]-ethylamino}- l-naphthylazo}-1 ,4-phtha1azinediol 2- [4- (Z-diethylaminoethylamino) -1-naphthy1azo]- phenazine 6-{6-chloro-4-[2-(1-pyrrolidinyD-ethylamino]-1- naphthylazo}-1,2,3 ,4-tetrahydro-2,3 -dimethyl- 1,4-phthalazinedione 3-diethylamino-7- [4- (2-diethylaminoethylarnino)- l-naphthylazo]-5-phenylphenazinium chloride, hydrochloride 6-4-2- [ethyl(2-piperidinoethyl)-amino] -ethylaminol-naphthylazo-1,4-phthalazinediol The intermediate 1-(dialkylaminoalkylamino)-naphthalenes employed herein are prepared from l-naphthylarnine or l-naphthol according to the procedures described under Examples 1 through 15.

Example 23 5-amino-8-methylquinoline (5.3 g., 0.03 mole) is diazotized and coupled into 7.6 g. (0.03 mole) of 4-(2- diethylaminoethyl) -1- [2-( l-naphthylamino) -ethyl]-piperidine according to the procedure outlined under Example 6 herein for the preparation of 1-diethylamino-3-[4-(3-pyridylazo)-l-naphthy1amino]-2-propanol, trihydrochloride. Crystallization of the crude dye from a mixture of 2- propanol and methanol gives the desired 5-{4-{2-[4-(2- diethylaminoethyl)-piperidino]-ethylamino}-l naphthylazo}-8-methylquinoline, trihydrochloride, of formula,

as a deep purple solid, M.P. -147 C.

Utilizing the preparative methods described under Examples 1 through 15 herein, the following related compounds can be prepared, starting from the appropriate substituted l-naphthylamine and aminoquinoline compound:

6-{4- [3-(4-methyl-1-piperazinyl) -2,2-dirnethylpropylamino] -1-naphthy1az0}-quinoline 3- [4- 3-dimethylamino-Z-methylpropylamino) -6-methyl- 1-naphthy1azo]-quinoline 3- [4- (4-diethylamino-2-isopropyl-l-methylbutylamino) l-naphthylazo] -quinoline 5- [4- 3-diethylaminopropylarnino) -1-naphthylazo] 7-piperidinomethyl-8-qu1inolino1 8- {4- 2-hydroxy-3 (methylpropylamino) -propy1amino] 1-naphthylazo}-6-quinolinol 5- Z-diethylaminoethylamin) -8- S-quinolylazo) -2- naphthoic acid 1-{2- [4- 3 quinolylazo) -1-naphthylamino] -ethyl}- 3-piperidinemethanol 6-ethoxy-5-meth0xy-8-}4- 2- 2-piperidinoetho ethylamino] -1-naphthylazo}-quinoline 3-{4- 2- 4-dimethylaminopiperidino) -ethylamino] 1-naphthylazo}-quinoline 5- Z-diethylaminoethylamino) -8- 5,6-dimeth0xy-8- quinolylazo) -2-naphthol 33 8-{4-{ [4-diethylaminomethyl)-cyclohexylmethyl] amino}- 1-naphthylazo}-5-methoxyquinoline 4- {4- [2- cyclopentylmethylamino) -ethylamino] -1- naphthylazo}-quinoline 4-(2-diethylaminoethyl)-1-[2-(1-naphthylamino)-ethyl]- piperidine, B.P. 208-209 C./O.2 mm., 11 1.5795, employed as a starting material in the above procedure, is prepared from N-(Z-bromoethyl)-1-naphthylamine, hydrobromide and 4-(2-diethylaminoethyl)-piperidine according to the method outlined under Example 3 herein for the preparation of l-1-diisopropyl-4-methyl-7-(l-naphthyl)- diethylenetriamine. The other substituted l-naphthylamine intermediates employed herein can be prepared from the appropriate l-naphthylamine or l-naphthol compound according to the procedures described under Examples 1 through 15.

Example 24 B-aminopyridine (4.7 g., 0.05 mole) is diazotized and coupled into 13.4 g. (0.05 mole) of 1-[3-(1-naphthylamino)-propyl]-piperidine according to the procedure outlined under Example 3 herein for the preparation of -{4-{2-[ (Z-diisopropylaminoethyl)-met.hylamino] ethylamino}-1-naphthylazo}-indazole. Crystallization of the crude dye from 2-propanol gives the desired 1-{3-[4-(3- pyridylazo) 1 naphthylamino1-propyl} piperidine, of

formula,

NH(C HmN as maroon crystals, M.P. 130-123 C.

Utilizing the preparative methods described under Examples 1 through 15 herein, the following related compounds can be prepared, starting from the appropriate substituted l-naphthylamine and aminopyridine:

5-[4-(2-diethylaminoethylamino) -1-naphthylazo] -2- methoxypyridine.

2-chloro-S- [4- Z-diethylaminoethylamino -1-naphthylazo] -pyridine.

decahydro-1-{2- [4- 3-pyridylazo) -1-naphthylamino] ethyl}-quinoline.

4-{5- [4- 2-morpholinoethylamino) -1-naphthylazo] -2- pyridyl}-morpholine.

3-{4-{2-{ {2- [Z-dimethylaminoethyl -methylamino] ethyl}-methylamino}-ethylamino}-1-naphthylazo}- pyridine.

1 -methyl-2-{2- [4-( 3-pyridylazo) -1-napthylamino] -ethyl}- piperidine.

3-{4- 5- diethylaminomethyl -tetrahydrofurfurylamino] l-naphthylazo}-pyridine. 3-[5-chloro-4-(Z-diethylaminoethylamino) -1-naphthy1- azo] -pyridine.

3- [4-(2-diethylaminoethylamino) -6-ethoxy-1-naphthylazo] -pyridin e.

1-{2- [4-(3-pyridylazo) -1-naphthylamino] -ethyl}-1- azaspiro [4.5] decane.

3- 4-( 2-dimethylaminoethylamino) -1-naphthylazo] pyridine, trihydrochloride.

2-{ {2-[4-(Z-methyl-S-pyridylazo) -1-naphthylamino]- ethyl}-pentylamino}-ethanol, trihydrochloride.

l-[3-(l-naphthylamine)-propyl]-piperidine, employed as a starting material in the above procedure, is prepared as follows: N-(3-hydroxypropyl)-l-naphthylamine is allowed to react with hydrobromic acid according to the method outlined under Example 3 herein for the preparation of N-(2-bromoethyl)-l-naphthylamine, hydrobromide. The intermediate N-(3-bromopropyl)-1-naphthylamine, hydrobromide, thus obtained melts at 152l54 C. This compound is subsequently allowed to react with piperidine according to the procedure described under Example 3 herein for the preparation of 1,1-diisopropyl- 4-methyl-7-(l-naphthyl)-diethylenetriamine to give the desired intermediate, 1-[3-(l-naphthylamino)-propyl]- piperidine, as off white crystals, M.P. 7072 C.

The other intermediate 1-(dialkylaminoalkylamino)- naphthalenes employed herein can be prepared from the appropriate l-naphthylarnine or l-naphthol according to the procedures described under Examples 1 through 15.

Example 25 S-aminobenzotriazole (13.4 g., 0.1 mole) is diazotized and coupled into 22.8 g. (0.1 mole) of N ,N -dimethyl- N -l-naphthyl-l,2-propanediamine according to the procedure outlined under Example 3 herein for the preparation of 5 {4 {2 [(2-diisopropylaminoethyl)-methylamino}-1-naphthylazo}-indazole. Crystallization of the crude dye from ethanol gives the desired 6-[4-(2-dimethylamino 1 methylethylamino)-1-naphthylazo]-1H-benzotriazole, of formula,

as orange-red crystals, M.P. 197l99 C.

Utilizing the preparative methods described under Examples 1 through 15 herein, the following related compounds can be prepared, starting from the appropriate substituted l-naphthylamine and aminotriazole, aminobenzotriazole, or aminotetrazole precursors:

6 [4- 2-diethylaminoethylamino) -l-naphthylazo] -1H- benzotriazole 6-amino-7-[4-(Z-diethylaminoethylamino) -1-naphthylazo] -1H-benzotriazole 5-{4-{2-14-(2-morpholinoethyl)-piperidino]-ethylarnino}- 1-naphthylazo}-lH-benzotriazole 4-[4-(3-dimethylaminopropylamino)-6-phenyl-l-naphthylazo] -1-methyl-lH-benzotriazole 4-amino-7-{4-[2-diethylamino-1-(methoxymethyl)- ethylamino]-1-naphthylazo} lH-benzotriazole 1-{2- [4-(s-triazol-3-ylazo) l-naphthylamino] -ethyl}-4- piperidinol 4- [4- 3-dimethylaminopropylamino) -5-sulfo-1-naphthylazo] -1H-benzotriazole-l-acetic acid 5-{4- [2,2-dimethyl-3-( l-pyrrolidinyl)-propylamino] -1- naphthylazo}-s-triazole-3-carboxylic acid.

5- [4-(Z-diethylaminoethylamino)-1-naphthylazo]-1H- tetrazole 6-{4-{3-[bis( 3-diethylaminopropyl)-amino] -propylamino}-1-naphthylazo}-lH-benzotriazole 3- [4-(Z-diethylaminoethylamino)-1-naphthylazo] s-triazole 5- [6-chloro-4-(2-diethylaminoethylamino)-1-naphthylazo]-1-methyl-1H-tetrazole 5-amino-4- [4-(Z-diethylaminoethylamino) -1-naphthylazo] -6-methyl-2-phenyl-2H-benzotriazole 3- [6-chloro-4- (Z-diethylaminoethylamino) -1-naphthylazo]-5-imino-1-phenyl-A -1,2,4-triazoline 6-{4-[5-(isopropylmethylamino)-pentylamino]-1- naphthylazo}-5-hydroxy-lH-benzotriazole-4 carboxylic acid 1-{{2- [4-( lH-benzotriazol-S-ylazo)-l-naphthylamino]- ethyl}-ethylamino}-2-methyl-2-propanol N ,N dimethyl N l-naphthyl-l,Z-pmpanediamine,

B.P. 118-120 C./ 0.2 mm., employed as a starting material in the above procedure, is prepared from l-naphthyl- 2,4-dimethoxy--aminopyrimidine (15.5 g., 0.09 mole) is diazotized and coupled into 24.3 g. (0.09 mole) of N,N- diisopropyl-N'-l-naphthylethylenediamine according to procedure described under Example 1 herein. The red crystalline dye that separates in the desired 5-[4-(2-diisopropylarninoethylamino) l-naphthylazo]-2,4-dimethoxypyrimidine, of formula,

Crystallization of the crude dye from acetone gives red needles, M.P. 157158 C.

In like manner, the following related compounds can be prepared, starting from equivalent quantities of the appropriate aminopyrimidine and l-(dialkylaminoalkylamino)-naphthalene compounds: 5-[4-(Z-diethylaminoethylamino)-1-naphthylazo]-2,4-

dimethoxypyrimidine, salt with (5,6,7,8-tetrahydro-1- methyl-Z-naphthyloxy) acetic acid 2,4-diethoxy-5-{4-{2-{4-[2-(4-methyl-l-piperazinyl)- ethyl]-piperidino}-ethylamino}-1-naphthy1azo}- pyrimidine 1- [4-(2,4-diphenoxy-S-pyrimidinylazo) -1-naphthylamino]-3-dipropylamino-2-propanol, pyromellitate 5-{4-[2-(isopropylmethylamino)-ethylamino]-1- naphthylazo}-2,4-dimethylpyrimidine, salt with 1,5-

naphthalenedisulfonic acid 5- 6-bromo-4-( Z-diethylaminoethylamino) -1-naphthylaZOJ-Z-methyIpyrimidine 5-{4-{2- (2-diisopropylaminoethyl -methylamino] ethylamino}-1-naphthylazo}-2,4-dimethoxypyrimidine, hydrochloride 1-{2-[4-(2,4-dimethoxy-5-pyrimidinylazo)-1-naphthylamino]-ethyl}-3-piperidinol 5-{4- 2- (cyclopentylmethylamino) -ethylamino] -1- naphthylazo}-4,6-dimethoxy-2-methylpyrimidine 5-{4-[S-(dimethylaminomethyl)-tetrahydrofurfurylamino] -1-naphthylazo}-4-methoxy-2-methy1- pyrimidine, terephthalate 5-[4-(4-diethylamino-l-methylbutylamino)-1- naphthylazo]-2,4-dimethoxypyrimidine, sulfate 4-chloro-5-{4- Z-diethylamino-ldiethylaminoethyl) ethylamino]-1-naphthylazo}-6-methoxy-2- methylpyrimidine 2,4-dimethoxy-5-{4-[Z-(tetrahydro-l-azepinyl)-ethylamino]-l-naphthylazo}-pyrimidine The starting material, N,N-diisopropyl-N-l-naphthylethylene diamine, is obtained as a yellow oil, B.P. 178- 179 C./0.9 mm., 11 1.57.82, by the condensation of l-naphthylamine and 2-diisopropylaminoethylchloride, hydrochloride according to the procedure outlined under Example 1 herein for the preparation of 1-(2-diethylaminoethylamino)-naphthalene.

The other intermediate 1-(dialkylaminoalkylamino)- naphthalenes employed herein can be prepared according to the procedures described under Examples 1 through 15 36 Example 27 N (2 diethylaminoethyl) N (4 amino 1 naphthyl)-trifiuoroacetamide, monohydrochloride (19.5 g., 0.05 mole) is diazotized at 0 C. according to the procedure described under Example 14 herein. Subsequently, a solution of 8.7 g., 0.05 mole) of 3-methyl-1- phenyl-S-pyrazolone in 200 ml. of water, 8.4 ml. of 6 N sodium hydroxide, and 4.2 g. of sodium bicarbonate is slowly added at 0-5 C. to the diazonium salt solution, 4.2 g. of sodium bicarbonate is added, and the mixture stirred at room temperature for 18 hours. The orange precipitate is collected by filtration, washed with water, dried, and crystallized from acetone. The intermediate N.- (2 diethylaminoethyl) 2,2,2 trifluoro N [4-(3- methyl 5 oxo 1 phenyl 2 pyrazolin 4 ylazo)- 1 naphthyl] acetamide thus obtained, of formula,

melts at 154-155 C.

A portion of the above amide (10 g.) is dissolved in 800 ml. of acetone. Water (10 ml.) and 30 ml. (0.06 mole) of 2 N sodium hydroxide solution are added, and the resulting mixture is stirred for 20 hours at room temperature. The mixture is filtered, and the filtrate evaporated to dryness in vacuo. The residue is extracted with ether and the combined ether extracts are washed successively with dilute ammonium hydroxide and saturated sodium chloride solution and dried over anhydrous magnesium sulfate. The ether solution is evaporated until crystallization begins, and the product is collected by filtration. Crystallization from 2-propanol gives the desired 4 [4 (2 diethylaminoethylamino) 1 naphthylazo] 3 methyl 1 phenyl 2 pyrazolin 5 one, of formula,

1-{ 3- [4- 3,5 -diamino- 1-phenyl-4-pyrazoly1azo) l naphthylamino -propyl }-piperidine.

3,5-diamino-4-{4- 2- isopropylmethylamino) -ethylamino] -7-chloro1-naphthylazo}-pyrazole.

The intermediate N-[4-pyrazolylazo-l-naphthyl)-N- (dialkylaminoalkyl) a,ct,a trifiuoroacetamides are prepared from the appropriate pyrazole compound and N-dialkylaminoalkyl N (4 amino 1 naphthyl) a,oz,utrifluoroacetamide in accordance with the methods described under Examples 2, 9, 14, and 29 herein.

Example 28 7-aminobenzo[f]quinoline (7.8 g., 0.04 mole) is diazotized and coupled into 9.1 g. (0.04 mole) of N-ethyl-N- methyl-N'-l-naphthylethylenediamine according to the procedure described under Example 3 herein. Crystallization of the red dye thus obtained from boiling 2-propanol gives the desired 7-{4-[2 (ethylmethylamino) ethylamino]-l-naphthylazo}-benzo[f]quinoline, of formula,

as maroon crystals, M.P. 182l84 C.

Utlizing procedures similar to those described under Examples 1 through 15 herein, the following related compounds can be prepared, starting from an appropriately substituted l-naphthylamine and hydroxy or amino benzoquinoline or phenanthridine compound.

4-{2-{l-{2-[4-(7-benzo[f]quinolinylazo) 1 naphthylamino]-ethyl}-4-piperidinyl}-ethyl}-l-piperazineethanol 10-{4-[2-(ethylpropylamino)-ethylamino]-6-methoxy 1- naphthylazo}-6-methylphenanthridine 8-[4-(Z-diethylaminoethylamino)-l-naphthylazo] benzo [f] quinoline 5-{4-{3-[(3-diethylaminopropyl) ethylamino] propylamino}-1-naphthylazo}-benzo[f]quinoline 6-[4-(4-diethylaminocyclohexylamino)-1 naphthylazo]- 4-methylbenzo [h] quinolin-2( 1H) -.one

3-[4-(Z-diethylaminoethylamino) 1 naphthylazo] 2- methylbenzo[h]quinolin-4-ol 2- (Z-diethylaminoethylamino] -1-{4- 3 (isopropylmethylamino)-propylamino]-7-methyl 1 naphthylazo} 6- methylphenanthridine 5-(2-diethylaminoethylamino)-6 (4 diethylaminoethylaminol-naphthylazo -benzo [f quinoline The starting material, N-ethyl-N-methyl-N'-1-naphthylethylenediamine, is a viscous yellow oil, B.P. 146147 C./0.4 mm., n 1.5990. This intermediate can be prepared from 1 naphthylamine and 2 (methylethylamino)-ethylchloride, hydrochloride according to the procedure described under Example 1 herein for the preparation of 1-(2 diethylaminoethylan1ino)-naphthaline. The other substituted l-naphthylamines employed herein are prepared according to procedures similar to those described under Examples 1 through 15.

Example 29 A solution of 11.7 g. (0.03 mole) of N-(Z-diethylaminoethyl) -N-(4-amino-1-naphthyl) -trifluoroacetamide, monohydrochloride, is diazotized according to the procedure described in Example 2 herein and coupled into a solution of 7.0 g. (0.03 mole) of N-(2-diethylaminoethyl)- 1,2,3,4-tetrahydroquinoline in 15 ml. of concentrated hydrochloric acid, ml. of water and g. of ice. After stirring for 2 hours at 0-5 C., 19.5 ml. of concentrated ammonium hydroxide and 100 ml. of water are added and the precipitate that separates is extracted with ether. The combined ether extracts are washed with water and then with saturated sodium chloride solution and dried over anhydrous magnesium sulfate. The ether is re moved in vacuo, and the intermediate trifiuoroacetamide is dissolved in 300 ml. of ethanol and is stirred with 30 ml. (0.060 mole) of 2 N sodium hydroxide in methanol and 30 ml. of water under nitrogen at room temperature for 24 hours. The mixture is treated with excess Dry Ice and 500 ml. of water and concentrated in vacuo to 500 ml. The red supernatant is decanted from the sticky red dye which separates and the dye is treated with 250 ml. of 2-propanol and 12 ml. (0.024 mole) of a 2 N Z-propanolhydrogen chloride mixture. One liter of anhydrous ether is then added slowly with stirring, depositing a red dye which crystallizes after 4 hours. Recrystallization from a methanol-ethyl acetate mixture gives the desired 1- (2-diethylaminoethy1) -6-[4-(2 diethylaminoethylamino) l-naphthylazo]-1,2,3,4-tetrahydroquinoline, dihydrochloride, of formula,

M.P. -1985 C.

In like manner, the following related compounds can be prepared, starting from the appropriate l-(dialkylaminoalkyl)-N-(4 amino-l-naphthyl) trifluoroacetamide and 1,2,3,4 tetrahydroquinoline, indoline, 1,2,3,4 tetrahydro-1,3-quinazoline, 3,4-dihydro-2H-1,4-benzoxazine, 2, 3-dihydro-1H-naphth[2,1]-p-oxazine, 1,2,3,4 tetrahydroquinoxaline, or 1,2,3,4-tetrahydrobenzo[h]quinoline via the N-[4 (heterocyclicazo-l-naphthyl]-N-(dialkylaminoalkylamino)-a,a,u-trifluoroacetamides:

6-[4-(Z-diethylaminoethylamino)-1-naphthylazo]-2,3 dihydro-1H-naphth[2,1]-p-oxazine, hydrochloride 6-[4-(Z-diethylaminoethylamino)-1-naphthylazo] 1,2,3,

4-tetrahydroquinoline, hydrochloride 5-[4-(2-diethylaminoethylamino)-1-naphthylazo] indo line, hydrochloride 7- [4- (Z-diethylaminoethylamino -1 -naphthylazo] -3,4 dihydro-2H-1,4-benzoxazine, hydrochloride 6-[4-(3-piperidinopropylamino)-1-naphthylazo]-3,4 dihydro-l (2H) -quinolineethanol, hydrochloride 5-{4-[2-(isopropylmethylamino)-ethylamino] 1 naphthylazo}-l-methylindoline, hydrochloride 1-(2-ethoxyethyl)-1,2,3,4-tetrahydro-6-[4-(2 piperidinoethylamino)-l-naphthylazo]-quinoline, hydrochloride 3-9 6-[4-(Z-diethylaminoethylamino)-l-naphthylazol 1,2,3, 4-tetrahydro-l ,3-quinazolinediethanol, hydrochloride -[4-(Z-diethylaminoethylamino)-7-methoxy 1 naphthylazo]-2-methylindoline, hydrochloride 5-chloro-1-(2-diethylaminoethyl)-8-[4 (Z-diethylaminoethylamino)-l-naphthylazo] 1,2,3,4 tetrahydro 6- methylquinoline, hydrochloride 3-{6-[4-(Z-diethylaminoethylamino)-1 naphthylazo] -l,2,

3,4-tetrahydro-2,7-dimethyl-1-quinolyl}-1,2 propanediol, hydrochloride 5-[6-chloro-4-(3 diethylamino 2,2 dirnethylpropyl amino)-l-naphthylazo]-1-(2 diethylaminoethyl) indoline, hydrochloride 6-[4-(Z-diethylaminoethylarnino)-1-naphthylazo] 1,2,3,

4*tetrahydroquinoxaline, hydrochloride 6-[4-(Z-diethylaminoethylamino)-1-naphthylazo] 1,2,3,

4-tetrahydrobenzo[h] quinoline, hydrochloride 6-{4-[2-(hexahydro 1 azepinylethylarnino] 1 naphthylazo}-1,2,3,4-tetrahydrolepidine, hydrochloride 6-[4-(Z-diethylaminoethylamino)-1-naphthylazo] 1,2,3, 4-tetrahydro-1,4,-dimethylquinoxaline, hydrochloride The other N-[4-(heterocyclicazo)-l-naphthyl]-N-(dialkyaminoalkylamino)-a,a,a-trifluoroacetamides are prepared in a similar manner from the appropriate aminoheterocyclic compounds and N-dialkylaminoalkyl-N-( lamino-l-naphthyl)-a,a,a-trifiuoroacetamides.

Example 30 3-amino-IO-ethylphenothiazine, 5,5-dioxide (0.85 g., 0.0031 mole) is diazotized and coupled into 0.84 g. (0.0031 mole of N,N,N',N'-tetramethyl-2-(l-naphthylamino)-l,3-propanediamine according to the procedure outlined under Example 6 herein for the preparation of ldiethylamino 3 [4 (3 pyridylazo) 1 naphthylaminoJ-Z-propanol, trihydrochloride. Purification of the crude dye from a mixture of acetone, ether, and ethanolic hydrogen chloride gives the desired 3-{4-[2-dimethylamino l (dimethylaminomethyl) ethylamino] 1- naphthylazo}-IO-ethylphenothiazine, 5,5-dioxide, trihydrochloride, of formula,

as a purple-brown hydrated solid, M.P. 195-197 C.

Utilizing the preparative methods outlined under Examples 1 through 15 herein, the following related compounds can be prepared, starting from the appropriate substituted l-naphthylamine and hydroxy or aminoheterocyclic compound:

2-[4-(2-diethylaminoethylamino)-1-naphthylazo]- dibenzo[b,f] l,4,5]-thiadiazepine, 11,11-dioxide. 3-hydroxy-2-{4-[2-(isopropylmethylamino)-ethylamino]- 1-nz1phthylazo}-phenazoxonium hydroxide, inner salt. 7-{4-[3-diethylamino-1-(2-diethylaminoethyl)-propylamino]-1-naphthylazo}-5H-[1]ber1zothiapyrano[2,3- clpyridin-S-one. 8-{4-{2-{2-[2-( l-pyrrolidinyl)-ethyl]-piperidino}- cthylamino}-1-naphthylazo}-4,9-thiophanthrenedione. 8- Z-diethylaminoethylamino)-5- lO-oxo-lOH-[ l benzothiapyrano 3 ,2-b] -pyridin-8-ylazo) -l-naphthoic acid. 3-{4-[2-diethylaminoethyl)-cyclopentylaminol]-1-naphthylazo}-7-dimethylamino-phenazathionium chloride. 3-imino-7-{4-{2- [4-( 1-methyl-4-piperidyl)-piperidino]- ethylamino}-l-naphthylazo}-3H-isophenoxazine. 8-[4-(Z-diethylaminoethylamino)-5-ethoxy-1-naphthylazo] -l0H- l ]-benzothiapyrano [3,2-b] pyridine.

8- [4- (4-diethy1amino-l ,2-dimethylbutylamino) -l-naphthylazo] -1OH- l -benzothiapyrano [3,2-c] pyridin-l 0- one.

6-{ 4- 3- (3 -diethylaminopropylthio -propylamino] -1- naphthylazo} -4,9-thiophanthrenedione.

7- [4- 2-diethylaminoethylamino 1 -naphthylazo -2,3- dihydro-2,6-dimethyl- 1 H-pyrrolo 3 ,4-c] pyridine.

3-diethylamino-7-{4- [3 3-diethylaminopropyoxy -proppylamino] -1-naphthylazo}-2-methylphenazoxoniumchloride.

9- [4- Z-diethylaminoethylamino 1 -naphthylazo] pyrido[ 1,2-a] benzimidazol-8-ol.

N,N,N,N'-tetramethyl-2-(l-naphthylamino)-l,3 propanediamine, B.P. 137-138 C./0.3 mm., m, 1.5836, employed as a starting material in the above preparation, is prepared from l-naphthol and l,3,-bis(dimethylamino)-2- propylamine according to the procedure outline under Example 8 herein for the preparation of 1-(3-dimethylaminopropylamino)-napthalene. The other intermediate l-naphylthylamines employed herein can be prepared from the appropriate l-naphthol or l-naphthylamine precursors according to the procedure described under Examples 1 through 15.

Example 31 5-amino-2-butoxypyridine (16.6 g,, 0.1 mole) is diazotized and coupled into 24.2 g. (0.1 mole) of 1-(2-diethylaminoethylamino)-naphthalene according to the procedure described under Example 3 herein for preparation of 5 {4 {2 [(2 diisopropylaminoethyl)-methylamino]-ethylamino}-1 naphthylazo} inadzole. Crystallization of the crude dye from ethanol gives the desired 2- butoxy 5 [4 (2 diethylaminoethylamino) 1 naphthylazo]-pyridine, of formula,

as orange-red crystals, M.P. 92-94 C.

Utilizing the preparative methods described under Examples 1 through 15 herein, the following related compounds can be prepared, starting from the appropriate substituted l-naphthylamine and aminopyridine or hydroxypyridine compound:

3-{4- 2- l-propyl-Z-pyrrolidinyl) -ethylamino] l -naphthylazo}-pyridine.

Z-benzyloxy-S- [4- (Z-diisopentylaminoethylamino) -1- naphthylazo -pyridine.

5- [6-chloro-4-(2-diethylaminoethylamino) -1-naphthylazo] -2-propoxypyridine.

3 4- 2- 2,5 -dimethyll-pyrrolidinyl -ethylamino] lnaphthylazo} -pyridine.

3 -{4- 2(Z-diethylaminoethylthio -ethylamino] -1- napthylazo} -pyridine.

8- 2-diethylaminoethylamino-S- 3-pyridylazo -2- naphthalenesulfonic acid.

1-methyl-4- {2- [4- 3-pyridylazo l -naphthylamino ethyl -piperazine.

5- [4- S-diethylaminooctylamino) -l-naphthylazo] -2- diimethylaminopyridine.

3 [4- 2-dihexylaminoethylamino l -naphthylazo] pyridine.

8-(6-ametamido-3-pyridylazo) -5-(2-diethylaminoethylamino) -2-naphthoic acid.

3-{4-[ l-(diethylaminomethyl -cyclohexylmethylamino]- 1-naphthylazo}-pyridine.

5- Z-diethylaminoethylamino -8- 6-methoxy-3-pyridylazo)-2-naphthol. 

1. A MEMBER SELECTED FROM THE GROUP CONSISTING OF A FREE BASE OF FORMULA 